Macrocyclic picolinamides compounds with fungicidal activity

ABSTRACT

The invention relates to compounds of macrocyclic picolinamides of Formula I suitable to control or prevent growth of fungi.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/885,409, and U.S. Provisional Patent ApplicationSer. No. 61/885,417, each filed Oct. 1, 2013, the disclosures of each ofwhich is expressly incorporated by reference herein.

BACKGROUND & SUMMARY

Fungicides are compounds, of natural or synthetic origin, which act toprotect and/or cure plants against damage caused by agriculturallyrelevant fungi. Generally, no single fungicide is useful in allsituations. Consequently, research is ongoing to produce fungicides thatmay have better performance, are easier to use, and cost less.

The present disclosure relates to macrocyclic picolinamides and theiruse as fungicides. The compounds of the present disclosure may offerprotection against ascomycetes, basidiomycetes, deuteromycetes andoomycetes.

One embodiment of the present disclosure may include compounds ofFormula I:

-   -   X is H, C(O)R₃, or CH₂OR₃;    -   Y is H, C(O)R₃, or Q;    -   Q is

-   -   R₁ is H, alkyl, alkenyl, aryl, —Si(R₅)₃, —C(O)R₆, each        substituted with 0, 1 or multiple R₆;    -   R₂ is CH₂R₈, aryl, alkyl, alkenyl, each substituted with 0, 1,        or multiple R₆;    -   R₃ is alkyl, alkoxy, benzyl, benzyloxy, each substituted with 0,        1, or multiple R₅;    -   R₄ is H, —C(O)R₇ or —CH₂OC(O)R₇;    -   R₅ is alkyl, halo, alkoxy;    -   R₆ is alkyl, alkenyl, halo, haloalkyl, alkoxy, aryl, heteroaryl,        heterocyclyl, thioalkyl, —C(O)R₅;    -   R₇ is alkyl or alkoxy, each substituted with 0, 1, or multiple        R₆;    -   R₈ is H, alkyl, alkenyl, aryl, heteroaryl, thioalkyl each        substituted with 0, 1, or multiple R₆.

Another embodiment of the present disclosure may include a fungicidalcomposition for the control or prevention of fungal attack comprisingthe compounds described above and a phytologically acceptable carriermaterial.

Yet another embodiment of the present disclosure may include a methodfor the control or prevention of fungal attack on a plant, the methodincluding the steps of applying a fungicidally effective amount of oneor more of the compounds described above to at least one of the fungus,the plant, and an area adjacent to the plant.

It will be understood by the those skilled in the art that the followingterms may include generic “R”-groups within their definitions, e.g.,“the term alkoxy refers to an —OR substituent”. It is also understoodthat within the definitions for the following terms, these “R” groupsare included for illustration purposes and should not be construed aslimiting or being limited by substitutions about Formula I.

The term “alkyl” refers to a branched, unbranched, or saturated cycliccarbon chain, including, but not limited to, methyl, ethyl, propyl,butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl and the like.

The term “alkenyl” refers to a branched, unbranched or cyclic carbonchain containing one or more double bonds including, but not limited to,ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclobutenyl,cyclopentenyl, cyclohexenyl, and the like.

The term “alkynyl” refers to a branched or unbranched carbon chaincontaining one or more triple bonds including, but not limited to,propynyl, butynyl and the like.

The term “aryl” refers to any aromatic, mono- or bi-cyclic, containing 0heteroatoms.

The term “heterocycle” refers to any aromatic or non-aromatic ring,mono- or bi-cyclic, containing one or more heteroatoms

The term “alkoxy” refers to an —OR substituent.

The term “cyano” refers to a —C≡N substituent.

The term “hydroxyl” refers to an —OH substituent.

The term “amino” refers to a —NH₂ substituent.

The term “arylalkoxy” refers to —O(CH₂)_(n)Ar where n is an integerselected from the list 1, 2, 3, 4, 5, or 6.

The term “haloalkoxy” refers to an —OR—X substituent, wherein X is Cl,F, Br, or I, or any combination thereof.

The term “haloalkyl” refers to an alkyl, which is substituted with Cl,F, I, or Br or any combination thereof.

The term “halogen” or “halo” refers to one or more halogen atoms,defined as F, Cl, Br, and I.

The term “nitro” refers to a —NO₂ substituent.

The term thioalkyl refers to an —SR substituent.

Throughout the disclosure, reference to the compounds of Formula I isread as also including diastereomers, enantiomers, and mixtures thereof.In another embodiment, Formula (I) is read as also including salts orhydrates thereof. Exemplary salts include, but are not limited to:hydrochloride, hydrobromide, and hydroiodide.

It is also understood by those skilled in the art that additionalsubstitution is allowable, unless otherwise noted, as long as the rulesof chemical bonding and strain energy are satisfied and the productstill exhibits fungicidal activity.

Another embodiment of the present disclosure is a use of a compound ofFormula I, for protection of a plant against attack by a phytopathogenicorganism or the treatment of a plant infested by a phytopathogenicorganism, comprising the application of a compound of Formula I, or acomposition comprising the compound to soil, a plant, a part of a plant,foliage, and/or roots.

Additionally, another embodiment of the present disclosure is acomposition useful for protecting a plant against attack by aphytopathogenic organism and/or treatment of a plant infested by aphytopathogenic organism comprising a compound of Formula I and aphytologically acceptable carrier material.

DETAILED DESCRIPTION

The compounds of the present disclosure may be applied by any of avariety of known techniques, either as the compounds or as formulationscomprising the compounds. For example, the compounds may be applied tothe roots or foliage of plants for the control of various fungi, withoutdamaging the commercial value of the plants. The materials may beapplied in the form of any of the generally used formulation types, forexample, as solutions, dusts, wettable powders, flowable concentrate, oremulsifiable concentrates.

Preferably, the compounds of the present disclosure are applied in theform of a formulation, comprising one or more of the compounds ofFormula I with a phytologically acceptable carrier. Concentratedformulations may be dispersed in water, or other liquids, forapplication, or formulations may be dust-like or granular, which maythen be applied without further treatment. The formulations can beprepared according to procedures that are conventional in theagricultural chemical art.

The present disclosure contemplates all vehicles by which one or more ofthe compounds may be formulated for delivery and use as a fungicide.Typically, formulations are applied as aqueous suspensions or emulsions.Such suspensions or emulsions may be produced from water-soluble,water-suspendible, or emulsifiable formulations which are solids,usually known as wettable powders; or liquids, usually known asemulsifiable concentrates, aqueous suspensions, or suspensionconcentrates. As will be readily appreciated, any material to whichthese compounds may be added may be used, provided it yields the desiredutility without significant interference with the activity of thesecompounds as antifungal agents.

Wettable powders, which may be compacted to form water-dispersiblegranules, comprise an intimate mixture of one or more of the compoundsof Formula I, an inert carrier and surfactants. The concentration of thecompound in the wettable powder may be from about 10 percent to about 90percent by weight based on the total weight of the wettable powder, morepreferably about 25 weight percent to about 75 weight percent. In thepreparation of wettable powder formulations, the compounds may becompounded with any finely divided solid, such as prophyllite, talc,chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein,gluten, montmorillonite clays, diatomaceous earths, purified silicatesor the like. In such operations, the finely divided carrier andsurfactants are typically blended with the compound(s) and milled.

Emulsifiable concentrates of the compounds of Formula I may comprise aconvenient concentration, such as from about 1 weight percent to about50 weight percent of the compound, in a suitable liquid, based on thetotal weight of the concentrate. The compounds may be dissolved in aninert carrier, which is either a water-miscible solvent or a mixture ofwater-immiscible organic solvents, and emulsifiers. The concentrates maybe diluted with water and oil to form spray mixtures in the form ofoil-in-water emulsions. Useful organic solvents include aromatics,especially the high-boiling naphthalenic and olefinic portions ofpetroleum such as heavy aromatic naphtha. Other organic solvents mayalso be used, for example, terpenic solvents, including rosinderivatives, aliphatic ketones, such as cyclohexanone, and complexalcohols, such as 2-ethoxyethanol.

Emulsifiers which may be advantageously employed herein may be readilydetermined by those skilled in the art and include various nonionic,anionic, cationic and amphoteric emulsifiers, or a blend of two or moreemulsifiers. Examples of nonionic emulsifiers useful in preparing theemulsifiable concentrates include the polyalkylene glycol ethers andcondensation products of alkyl and aryl phenols, aliphatic alcohols,aliphatic amines or fatty acids with ethylene oxide, propylene oxidessuch as the ethoxylated alkyl phenols and carboxylic esters solubilizedwith the polyol or polyoxyalkylene. Cationic emulsifiers includequaternary ammonium compounds and fatty amine salts. Anionic emulsifiersinclude the oil-soluble salts (e.g., calcium) of alkylaryl sulphonicacids, oil-soluble salts or sulfated polyglycol ethers and appropriatesalts of phosphated polyglycol ether.

Representative organic liquids which may be employed in preparing theemulsifiable concentrates of the compounds of the present disclosure arethe aromatic liquids such as xylene, propyl benzene fractions; or mixednaphthalene fractions, mineral oils, substituted aromatic organicliquids such as dioctyl phthalate; kerosene; dialkyl amides of variousfatty acids, particularly the dimethyl amides of fatty glycols andglycol derivatives such as the n-butyl ether, ethyl ether or methylether of diethylene glycol, the methyl ether of triethylene glycol,petroleum fractions or hydrocarbons such as mineral oil, aromaticsolvents, paraffinic oils, and the like; vegetable oils such as soy beanoil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconutoil, corn oil, cotton seed oil, linseed oil, palm oil, peanut oil,safflower oil, sesame oil, tung oil and the like; esters of the abovevegetable oils; and the like. Mixtures of two or more organic liquidsmay also be employed in the preparation of the emulsifiable concentrate.Organic liquids include xylene, and propyl benzene fractions, withxylene being most preferred in some cases. Surface-active dispersingagents are typically employed in liquid formulations and in an amount offrom 0.1 to 20 percent by weight based on the combined weight of thedispersing agent with one or more of the compounds. The formulations canalso contain other compatible additives, for example, plant growthregulators and other biologically active compounds used in agriculture.

Aqueous suspensions comprise suspensions of one or more water-insolublecompounds of Formula I, dispersed in an aqueous vehicle at aconcentration in the range from about 1 to about 50 weight percent,based on the total weight of the aqueous suspension. Suspensions areprepared by finely grinding one or more of the compounds, and vigorouslymixing the ground material into a vehicle comprised of water andsurfactants chosen from the same types discussed above. Othercomponents, such as inorganic salts and synthetic or natural gums, mayalso be added to increase the density and viscosity of the aqueousvehicle.

The compounds of Formula I can also be applied as granular formulations,which are particularly useful for applications to the soil. Granularformulations generally contain from about 0.5 to about 10 weightpercent, based on the total weight of the granular formulation of thecompound(s), dispersed in an inert carrier which consists entirely or inlarge part of coarsely divided inert material such as attapulgite,bentonite, diatomite, clay or a similar inexpensive substance. Suchformulations are usually prepared by dissolving the compounds in asuitable solvent and applying it to a granular carrier which has beenpreformed to the appropriate particle size, in the range of from about0.5 to about 3 mm. A suitable solvent is a solvent in which the compoundis substantially or completely soluble. Such formulations may also beprepared by making a dough or paste of the carrier and the compound andsolvent, and crushing and drying to obtain the desired granularparticle.

Dusts containing the compounds of Formula I may be prepared byintimately mixing one or more of the compounds in powdered form with asuitable dusty agricultural carrier, such as, for example, kaolin clay,ground volcanic rock, and the like. Dusts can suitably contain fromabout 1 to about 10 weight percent of the compounds, based on the totalweight of the dust.

The formulations may additionally contain adjuvant surfactants toenhance deposition, wetting and penetration of the compounds onto thetarget crop and organism. These adjuvant surfactants may optionally beemployed as a component of the formulation or as a tank mix. The amountof adjuvant surfactant will typically vary from 0.01 to 1.0 percent byvolume, based on a spray-volume of water, preferably 0.05 to 0.5 volumepercent. Suitable adjuvant surfactants include, but are not limited toethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols,salts of the esters or sulphosuccinic acids, ethoxylatedorganosilicones, ethoxylated fatty amines, blends of surfactants withmineral or vegetable oils, crop oil concentrate (mineral oil(85%)+emulsifiers (15%)); nonylphenol ethoxylate;benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleumhydrocarbon, alkyl esters, organic acid, and anionic surfactant; C₉-C₁₁alkylpolyglycoside; phosphated alcohol ethoxylate; natural primaryalcohol (C₁₂-C₁₆) ethoxylate; di-sec-butylphenol EO-PO block copolymer;polysiloxane-methyl cap; nonylphenol ethoxylate+urea ammonium nitrrate;emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate(8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99. Theformulations may also include oil-in-water emulsions such as thosedisclosed in U.S. patent application Ser. No. 11/495,228, the disclosureof which is expressly incorporated by reference herein.

The formulations may optionally include combinations that contain otherpesticidal compounds. Such additional pesticidal compounds may befungicides, insecticides, herbicides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present disclosure in the mediumselected for application, and not antagonistic to the activity of thepresent compounds. Accordingly, in such embodiments, the otherpesticidal compound is employed as a supplemental toxicant for the sameor for a different pesticidal use. The compounds of Formula I and thepesticidal compound in the combination can generally be present in aweight ratio of from 1:100 to 100:1.

The compounds of the present disclosure may also be combined with otherfungicides to form fungicidal mixtures and synergistic mixtures thereof.The fungicidal compounds of the present disclosure are often applied inconjunction with one or more other fungicides to control a wider varietyof undesirable diseases. When used in conjunction with otherfungicide(s), the presently claimed compounds may be formulated with theother fungicide(s), tank-mixed with the other fungicide(s) or appliedsequentially with the other fungicide(s). Such other fungicides mayinclude 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol,8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin,Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis,Bacillus subtilis strain QST713, benalaxyl, benomyl,benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt,bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen,blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole,bupirimate, calcium polysulfide, captafol, captan, carbendazim,carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil,chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate,copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprousoxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil,dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate),dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran,diethofencarb, difenoconazole, difenzoquat ion, diflumetorim,dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton,dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine,dodine free base, edifenphos, enestrobin, enestroburin, epoxiconazole,ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol,fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil,fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate,fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph,fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole,flusilazole, flusulfamide, flutianil, flutolanil, flutriafol,fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium,fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates,GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalilsulfate, imibenconazole, iminoctadine, iminoctadine triacetate,iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone,iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam,isotianil, kasugamycin, kasugamycin hydrochloride hydrate,kresoxim-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb,mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride,mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam,metam-ammonium, metam-potassium, metam-sodium, metconazole,methasulfocarb, methyl iodide, methyl isothiocyanate, metiram,metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam,nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fattyacids), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate,oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen,pentachlorophenol, pentachlorophenyl laurate, penthiopyrad,phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin,polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassiumhydroxyquinoline sulfate, probenazole, prochloraz, procymidone,propamocarb, propamocarb hydrochloride, propiconazole, propineb,proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin,pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox,pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen,quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam,simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodiumpentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils,tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole,thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl,tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole,tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram,zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp.,Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp.,(RS)—N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide,1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate,1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane,2-(2-heptadecyl-2-imidazolin-1-yl)ethanol,2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide,2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride,2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine,4-(2-nitroprop-1-enyl)phenyl thiocyanateme, ampropylfos, anilazine,azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox,bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl,bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmiumcalcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone,chloraniformethan, chlorfenazole, chlorquinox, climbazole, copperbis(3-phenylsalicylate), copper zinc chromate, cufraneb, cuprichydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram,decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol,dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin,drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf,fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole,furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin,halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos,isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam,methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride,myclozolin, N-3,5-dichlorophenyl-succinimide,N-3-nitrophenylitaconimide, natamycin,N-ethylmercurio-4-toluenesulfonanilide, nickelbis(dimethyldithiocarbamate), OCH, phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb;prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor,pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole,rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor,thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid,triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, andany combinations thereof.

Additionally, the compounds described herein may be combined with otherpesticides, including insecticides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present disclosure in the mediumselected for application, and not antagonistic to the activity of thepresent compounds to form pesticidal mixtures and synergistic mixturesthereof. The fungicidal compounds of the present disclosure may beapplied in conjunction with one or more other pesticides to control awider variety of undesirable pests. When used in conjunction with otherpesticides, the presently claimed compounds may be formulated with theother pesticide(s), tank-mixed with the other pesticide(s) or appliedsequentially with the other pesticide(s). Typical insecticides include,but are not limited to: 1,2-dichloropropane, abamectin, acephate,acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile,alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin,allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan,amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine,athidathion, azadirachtin, azamethiphos, azinphos-ethyl,azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin,bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin,bifenthrin, bioallethrin, bioethanomethrin, biopermethrin,bistrifluoron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT,bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb,butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calciumarsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl,carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion,carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole,chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeformhydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim,chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos,chromafenozide, cinerin I, cinerin II, cinerins, cismethrin,cloethocarb, closantel, clothianidin, copper acetoarsenite, copperarsenate, copper naphthenate, copper oleate, coumaphos, coumithoate,crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos,cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin,cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT,decarbofuran, deltamethrin, demephion, demephion-O, demephion-S,demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S,demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos,diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos,dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor,dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos,dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran,diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton,dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium,DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate,EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane,eprinomectin, esdepalléthrine, esfenvalerate, etaphos, ethiofencarb,ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate,ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide,etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor,fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb,fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion,fenthion, fenthion-ethyl, fenvalerate, flpronil, flonicamid,flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim,flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, formetanatehydrochloride, formothion, formparanate, formparanate hydrochloride,fosmethilan, fospirate, fosthietan, furathiocarb, furethrin,gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD,heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon,hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin,indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos,isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane,isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos,juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan,kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos,lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben,mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride,mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion,methiocarb, methocrotophos, methomyl, methoprene, methoxychlor,methoxyfenozide, methyl bromide, methyl isothiocyanate,methylchloroform, methylene chloride, metofluthrin, metolcarb,metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime,mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap,morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine,nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron,noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos,oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl,penfluoron, pentachlorophenol, permethrin, phenkapton, phenothrin,phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor,phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos,pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite,potassium thiocyanate, pp′-DDT, prallethrin, precocene I, precocene II,precocene III, primidophos, profenofos, profluralin, promacyl,promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos,prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos,pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben,pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate,pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl,quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla,schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodiumfluoride, sodium hexafluorosilicate, sodium thiocyanate, sophamide,spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron,sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfurylfluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide,tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP,terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos,tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiacloprid,thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate,thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium,thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin,transfluthrin, transpermethrin, triarathene, triazamate, triazophos,trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron,trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb,zeta-cypermethrin, zolaprofos, and any combinations thereof.

Additionally, the compounds described herein may be combined withherbicides that are compatible with the compounds of the presentdisclosure in the medium selected for application, and not antagonisticto the activity of the present compounds to form pesticidal mixtures andsynergistic mixtures thereof. The fungicidal compounds of the presentdisclosure may be applied in conjunction with one or more herbicides tocontrol a wide variety of undesirable plants. When used in conjunctionwith herbicides, the presently claimed compounds may be formulated withthe herbicide(s), tank-mixed with the herbicide(s) or appliedsequentially with the herbicide(s). Typical herbicides include, but arenot limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 3,4-DA; 2,4-DB; 3,4-DB;2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor,acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim,allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone,amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl,amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton,atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC,beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate,bensulfuron, bensulide, bentazone, benzadox, benzfendizone, benzipram,benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron,bicyclopyrone, bifenox, bilanafos, bispyribac, borax, bromacil,bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon,butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron,butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole,calcium chlorate, calcium cyanamide, cambendichlor, carbasulam,carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA, CEPC,chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine,chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop,chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen,chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham,chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin,cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop,clomazone, clomeprop, cloprop, cloproxydim, clopyralid, cloransulam,CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron,cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron,cyhalofop, cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon,dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba,dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P,diclofop, diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron,difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate,dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano,dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb,dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron,DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon,esprocarb, ethalfluralin, ethametsulfuron, ethidimuron, ethiolate,ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid,etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P,fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, ferroussulfate, flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop,fluazifop-P, fluazolate, flucarbazone, flucetosulfuron, fluchloralin,flufenacet, flufenican, flufenpyr, flumetsulam, flumezin, flumiclorac,flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen,fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil,flupropanate, flupyrsulfuron, fluridone, fluorochloridone, fluoroxypyr,flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen,glufosinate, glufosinate-P, glyphosate, halosafen, halosulfuron,haloxydine, haloxyfop, haloxyfop-P, hexachloroacetone, hexaflurate,hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin,imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil,iodomethane, iodosulfuron, ioxynil, ipazine, ipfencarbazone, iprymidam,isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin,isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole,isoxapyrifop, karbutilate, ketospiradox, lactofen, lenacil, linuron,MAA, MAMA, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb,mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam,metamifop, metamitron, metazachlor, metazosulfuron, metflurazon,methabenzthiazuron, methalpropalin, methazole, methiobencarb,methiozolin, methiuron, methometon, methoprotryne, methyl bromide,methyl isothiocyanate, methyldymron, metobenzuron, metobromuron,metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate,monalide, monisouron, monochloroacetic acid, monolinuron, monuron,morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon,nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen,norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene,orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon,oxasulfuron, oxaziclomefone, oxyfluorfen, parafluoron, paraquat,pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol,pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham,phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate,picloram, picolinafen, pinoxaden, piperophos, potassium arsenite,potassium azide, potassium cyanate, pretilachlor, primisulfuron,procyazine, prodiamine, profluazol, profluralin, profoxydim,proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop,propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron,propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor,pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate,pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor,pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac,pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine,quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron,saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim,siduron, simazine, simeton, simetryn, SMA, sodium arsenite, sodiumazide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone,sulfometuron, sulfosulfuron, sulfuric acid, sulglycapin, swep, TCA,tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim,terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn,tetrafluoron, thenylchlor, thiazafluoron, thiazopyr, thidiazimin,thidiazuron, thiencarbazone-methyl, thifensulfuron, thiobencarb,tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone,tri-allate, triasulfuron, triaziflam, tribenuron, tricamba, triclopyr,tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron,trifop, trifopsime, trihydroxytriazine, trimeturon, tripropindan,tritac, tritosulfuron, vernolate, and xylachlor.

Another embodiment of the present disclosure is a method for the controlor prevention of fungal attack. This method comprises applying to thesoil, plant, roots, foliage, or locus of the fungus, or to a locus inwhich the infestation is to be prevented (for example applying to cerealor grape plants), a fungicidally effective amount of one or more of thecompounds of Formula I. The compounds are suitable for treatment ofvarious plants at fungicidal levels, while exhibiting low phytotoxicity.The compounds may be useful both in a protectant and/or an eradicantfashion.

The compounds have been found to have significant fungicidal effectparticularly for agricultural use. Many of the compounds areparticularly effective for use with agricultural crops and horticulturalplants.

It will be understood by those in the art that the efficacy of thecompound for the foregoing fungi establishes the general utility of thecompounds as fungicides.

The compounds have broad ranges of activity against fungal pathogens.Exemplary pathogens may include, but are not limited to, causing agentof wheat leaf blotch (Mycosphaerella graminicola; impect stage: Septoriatritici), wheat brown rust (Puccinia triticina), wheat stripe rust(Puccinia striiformis), scab of apple (Venturia inaequalis), powderymildew of grapevine (Uncinula necator), barley scald (Rhynchosporiumsecalis), blast of rice (Magnaporthe grisea), rust of soybean(Phakopsora pachyrhizi), glume blotch of wheat (Leptosphaeria nodorum),powdery mildew of wheat (Blumeria graminis f sp. tritici), powderymildew of barley (Blumeria graminis f. sp. hordei), powdery mildew ofcucurbits (Erysiphe cichoracearum), anthracnose of cucurbits (Glomerellalagenarium), leaf spot of beet (Cercospora beticola), early blight oftomato (Alternaria solani), and spot blotch of barley (Cochliobolussativus). The exact amount of the active material to be applied isdependent not only on the specific active material being applied, butalso on the particular action desired, the fungal species to becontrolled, and the stage of growth thereof, as well as the part of theplant or other product to be contacted with the compound. Thus, all thecompounds, and formulations containing the same, may not be equallyeffective at similar concentrations or against the same fungal species.

The compounds are effective in use with plants in a disease-inhibitingand phytologically acceptable amount. The term “disease-inhibiting andphytologically acceptable amount” refers to an amount of a compound thatkills or inhibits the plant disease for which control is desired, but isnot significantly toxic to the plant. This amount will generally be fromabout 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm beingpreferred. The exact concentration of compound required varies with thefungal disease to be controlled, the type of formulation employed, themethod of application, the particular plant species, climate conditions,and the like. A suitable application rate is typically in the range fromabout 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per squaremeter, g/m²).

Any range or desired value given herein may be extended or alteredwithout losing the effects sought, as is apparent to the skilled personfor an understanding of the teachings herein.

The compounds of Formula I may be made using well-known chemicalprocedures. Intermediates not specifically mentioned in this disclosureare either commercially available, may be made by routes disclosed inthe chemical literature, or may be readily synthesized from commercialstarting materials utilizing standard procedures.

General Schemes

The following schemes illustrate approaches to generating picolinamidecompounds of Formula (I). The following descriptions and examples areprovided for illustrative purposes and should not be construed aslimiting in terms of substituents or substitution patterns.

Compounds of Formula 1.3, where R₂ is as originally defined, can beprepared by the method shown in Scheme 1, steps a-b. Compounds ofFormula 1.1, where R₈ is as originally defined and R₉ is alkyl oralkoxy, can be prepared from compounds of Formula 1.0, where R₈ is asoriginally defined, by treatment with an alkoxy borane such as pinacolborane in the presence of a nickel catalyst, such asbis(cyclooctadiene)nickel(0) (Ni(cod)₂), as described by Ely, R. J.;Morken, J. P. J. Am. Chem. Soc. 2010, 132, 2534-2535, in a solvent suchas toluene, and at a temperature between 0 and 23° C. Alternatively,compounds of Formula 1.1, where R₈ is as originally defined and R₉ isalkyl or alkoxy can be prepared as reported in Brown, H. C.; Bhat, K.S.; Randad, R. S. J. Org. Chem. 1989, 54, 1570. Compounds of Formula1.3, where R₂ is as originally defined, can be prepared from compoundsof Formula 1.1, where R₈ is as originally defined and R₉ is as definedabove by treatment with a benzyl (Bn) or para-methoxybenzyl (PMB)protected lactate-derived aldehyde such as compound 1.2, prepared asdescribed in Cheng and Brookhart Angew. Chem. Int. Ed. 2012, 51,9422-9424 (see Takai, K.; Heathcock, C. H. J. Org. Chem. 1985, 50,3247-3251 for characterization of Bn aldehyde and Terashima et al. Bull.Chem. Soc. Jpn. 1989, 62, 3038-3040 for characterization of PMBaldehyde).

Compounds of Formulas 2.0, 2.1, and 2.2 can be prepared using themethods shown in Scheme 2, steps a-c. Compounds of Formula 2.0, where R₁is aryl and R₂ is as originally defined, can be prepared by the methodshown in a, from compounds of Formula 1.3, where R₂ is as originallydefined, by treatment with a triarylbismuth reagent, prepared accordingto the methods described by Hassan, A. et. al. Organometallics 1996, 15,5613-5621, Moiseev, D. V. et al. J. Organomet. Chem. 2005, 690,3652-3663, or Sinclair, P. J. et al. Bioorg. Med. Chem. Lett. 1995, 5,1035-1038, in the presence of a copper catalyst, such asdiacetoxycopper, and an amine base, such asN,N-dicyclohexyl-methylamine, in an aprotic solvent such as toluene at20-40° C. Compounds of Formula 2.1, where R₁ is alkyl and R₂ is asoriginally defined, can be prepared from compounds of Formula 1.3, whereR₂ is as originally defined, by treatment with a base, such as sodiumhydride (NaH), in an aprotic solvent such as tetrahydrofuran (THF),followed by treatment with an alkyl halide or sulfonate, such asisobutyl toluenesulfonate at 0-22° C., as shown in b. Compounds ofFormula 2.2, where R₁ is silyl and R₂ is as originally defined, can beprepared from compounds of Formula 1.3, where R₂ is as originallydefined, by treatment with a silyl trifluoromethanesulfonate, such astriisopropyl trifluoromethanesulfonate, in the presence of a base, suchas 2,6-lutidine, in a solvent such as dichloromethane (CH₂Cl₂, DCM) at areduced temperature, such as 0° C., as shown in c.

Compounds of Formula 3.2, where R₁ and R₂ are as originally defined andY is tert-butoxy carbonyl (Boc), can be prepared by the method shown inScheme 3. Compounds of Formula 3.2 can be prepared from compounds ofFormula 3.0, where R₁ and R₂ are as originally defined, by treatmentwith an alkylborane reagent, such as 9-borabicyclo[3.3.1]nonane (9-BBN),in a solvent such as THF at 20-50° C., followed by treatment with anaqueous base, such as potassium phosphate (K₃PO₄), and a bromoacrylate,such as a compound of Formula 3.1 where Y is Boc, prepared as in Singhet al. Org. Lett. 2003, 17, 3155-3158, and a catalyst, such as[1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (PdCl₂(dppf))at 20-55° C.

Compounds of Formula 4.0, where R₁ and R₂ are as originally defined andY is Boc, can be prepared by the method shown in Scheme 4. Compounds ofFormula 4.0 can be prepared from compounds of Formula 3.2, where R₁ andR₂ are as originally defined and Y is Boc, by treatment with hydrogen(15-200 psi) in the presence of a catalyst such as1,2-bis[(2S,5S)-2,5-diethyl-phospholano]benzene(1,5-cyclooctadiene)rhodium(I)trifluoromethanesulfonate ((S,S)-Et-DUPHOS-Rh) in an alcoholic solventsuch as methanol (MeOH).

Compounds of Formula 5.3, where R₁ and R₂ are as originally defined andY is Boc can be prepared through a variety of methods, as shown inScheme 5, steps a-c. Compounds of Formula 5.0 and 5.1, where R₁ and R₂are as originally defined and Y is Boc, can be prepared from compoundsof Formula 4.0, where R₁ and R₂ are as originally defined, Y is Boc, andthe alcohol is protected as the PMB ether, by treatment with an oxidant,such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in an solventmixture such as DCM and water (H₂O), as shown in a. Compounds of Formula5.2, where R₁ and R₂ are as originally defined and Y is Boc, can beprepared from compounds of Formula 4.0, where R₁ and R₂ are asoriginally defined, Y is Boc, and the alcohol is protected as the Bnether, by hydrogenolysis, i.e., treatment with hydrogen (H₂; 15-500 psi)in the presence of a catalyst, such as 5% or 10% w/w palladium/carbon(Pd/C), in a solvent such as THF, as shown in b. Compounds of Formula5.3, where R₁ and R₂ are as originally defined and Y is Boc, can beprepared from compounds of Formulas 5.0 and 5.2, where R₁, R₂, and Y areas defined above and the acid is protected as methyl (Me) ester, bytreatment with a base such as lithium hydroxide (LiOH) in a mixture ofH₂O and a solvent such as THF, as shown in c. Compounds of Formula 5.3,where R₁ and R₂ are as originally defined and Y is Boc, can also beprepared from compounds of Formula 5.1, where R₁, R₂, and Y are asdefined above and the acid is protected as the Bn ester, byhydrogenolysis or saponification, as shown in b and c, respectively.Alternatively, compounds of Formula 5.3, where R₁ and R₂ are asoriginally defined and Y is Boc, can be prepared directly from compoundsof Formula 4.0, where R₁, R₂, and Y are as defined above and the alcoholand acid are protected as the Bn ether and Bn ester, respectively, bythe hydrogenolysis conditions described in b.

Compounds of Formula 6.0, where R₁ and R₂ are as originally defined andY is Boc, can be prepared from compounds of Formula 5.3, where R₁ and R₂are as originally defined and Y is Boc, by the addition of a solution ofcompounds of Formula 5.3 in a halogenated solvent such as DCM or anaromatic solvent such as toluene to a mixture of a base, such as DMAP,and an anhydride, such as 2-methyl-6-nitrobenzoic anhydride (MNBA), ineither a halogenated solvent such as DCM or an aromatic solvent such astoluene over a period of 4-12 hours, as shown in Scheme 6.

Compounds of Formula 7.1 can be prepared according to the methods shownin Scheme 7, steps a-b. Compounds of Formula 7.0, where R₁ istriisopropylsilyl (TIPS), R₂ is as originally defined, Y is Boc, and Xis methoxymethyl (MOM) can be prepared from compounds of Formula 6.0,where R₁, R₂, and Y are as defined above, by treatment with an aldehyde,such as paraformaldehyde, in a solvent such as DCM in the presence of asilyl chloride, such as trimethylsilyl chloride, at a reducedtemperature such as 0° C., followed by addition of a solution of a basesuch as triethylamine, in an alcoholic solvent such as methanol, asshown in a. Compounds of Formula 7.1, where R₁ is H and R₂, X, and Y areas defined above, can be prepared from compounds of Formula 7.0, whereR₁, R₂, X, and Y are as defined above, by treatment with a fluoride saltsuch as tetra-N-butylammonium fluoride (TBAF), in a solvent such as THF,as shown in b.

Compounds of Formulas 8.0-8.8 can be prepared through the methods shownin Scheme 8, steps a-g. Compounds of Formula 8.0, where R₁ is allyloxy,R₂ is as originally defined, X is MOM, and Y is Boc, can be preparedfrom compounds of Formula 7.1, where R₁ is H, R₂, X, and Y are asdefined above, by treatment with an allyl carbonate, such as atert-butyl (allyl) carbonate or a symmetric (allyl) carbonate, such asbis(2-methylallyl) carbonate, in the presence of a palladium catalystand ligand, for example tris(dibenzylideneacetone)-dipalladium(0)(Pd₂(dba)₃) and 1,1′-bis(diphenylphosphino)ferrocene (dppf), in a polaraprotic solvent like tetrahydrofuran (THF) at an elevated temperaturesuch as 60° C., as shown in a. Compounds of Formula 8.1, where R₁ isalkyl, R₂ is as originally defined, X is MOM, and Y is Boc, can beprepared from compounds of Formula 8.0, where R₁, R₂, X, and Y aredefined as above, by treatment with H₂ (15-200 psi) in the presence of acatalyst, such as 5% or 10% w/w Pd/C in a solvent such as EtOAc, asshown in b. Compounds of Formula 8.2, where R₁ is an aliphatic aldehydeand R₂, X, and Y are as defined above, can be prepared from compounds ofFormula 8.0, where R₁, R₂, X, and Y are as defined above, by treatmentwith ozone in the presence of a base, such as sodium bicarbonate(NaHCO₃) in a mixture of a halogenated and an alcoholic solvent, such asDCM and MeOH, as shown in c. Compounds of Formula 8.3, where R₁ isfluorinated alkyl and R₂, X, and Y are as defined above, can be preparedfrom compounds of Formula 8.2, where R₁, R₂, X, and Y are as definedabove, by treatment with a fluorinating reagent, such asbis(2-methoxyethyl)aminosulfur trifluoride (Deoxo-Fluor®) in a solventsuch as DCM, as shown in d.

Compounds of Formula 8.4, where R₁ is an vinylogous ester, R₂ is asoriginally defined, X is MOM, and Y is Boc, can be prepared fromcompounds of Formula 7.1, where R₁ is H, R₂, X, and Y are as definedabove, by treating solutions of the compounds of Formula 7.1 in asolvent such as DCM with a catalytic amount of1,4-diazabicyclo[2.2.2]octane (DABCO), followed by addition of aconjugated alkyne, such as but-3-yn-2-one at a reduced temperature, forexample 0° C., as shown in e. Compounds of Formula 8.5, where R₁ is analiphatic ketone, R₂ is as originally defined, X is MOM, and Y is Boc,can be prepared from compounds of Formula 8.4, where R₁, R₂, X, and Yare as defined above, by the reductive conditions described in b.Compounds of Formula 8.6, where R₁ is fluorinated alkyl, R₂ is asoriginally defined, X is MOM, and Y is Boc, can be prepared fromcompounds of Formula 8.5, where R₁, R₂, X, and Y are defined as above,by the fluorination conditions described in d.

Compounds of Formula 8.7, where R₁ is acyl, R₂ is as originally defined,X is MOM, and Y is Boc, can be prepared from compounds of Formula 7.1,where R₁ is H, R₂ is as originally defined, X is MOM, and Y is Boc, bytreatment with a base such as triethylamine and a catalyst such as(DMAP) in a solvent such as DCM, followed by treatment with an acidchloride, as shown in f.

Compounds of Formula 8.8, where R₁ is alkyl, R₂ is as originallydefined, X is MOM, and Y is Boc, can be prepared from compounds ofFormula 7.1, where R₁ is H, R₂ is as originally defined, X is MOM, and Yis Boc, by treatment with a base, such as1,8-bis(dimethylamino)naphthalene (Proton Sponge®) and an alkylatingagent, such as trimethyloxonium tetrafluoroborate, in a solvent such asDCM, as shown in g.

Compounds of Formula 9.1, where R₁ is as originally defined and Y isBoc, can be prepared by the method shown in Scheme 9. Compounds ofFormula 9.1 can be prepared from compounds of Formula 9.0, where R₁ isas originally defined and Y is Boc, by treatment with a fluoride salt,such as TBAF, in a solvent such as THF.

Compounds of Formulas 10.0-10.7 can be prepared through the methodsshown in Scheme 10, steps a-h. Compounds of Formula 10.0, where R₁ is asoriginally defined and Y is Boc, can be prepared from compounds ofFormula 9.1, where R₁ is as originally defined and Y is Boc, bytreatment with a triarylbismuth reagent, prepared according to themethods described by Hassan, A. et. al. Organometallics 1996, 15,5613-5621, Moiseev, D. V. et al. J. Organomet. Chem. 2005, 690,3652-3663, or Sinclair, P. J. et al. Bioorg. Med. Chem. Lett. 1995, 5,1035-1038, in the presence of a copper catalyst, such asdiacetoxycopper, and an amine base, such asN,N-dicyclohexyl-methylamine, in an aprotic solvent such as toluene atan elevated temperature of about 50° C., as shown in a. Compounds ofFormula 10.1, where R₁ is as originally defined and Y is Boc, can beprepared from compounds of Formula 9.1, where R₁ and Y are as definedabove, by treatment with a base such as Proton Sponge® followed by analkylating agent, such as trimethyloxonium tetrafluoroborate, in asolvent such as DCM, as shown in b. Compounds of Formula 10.2, where R₁is as originally defined and Y is Boc, can be prepared from compounds ofFormula 9.1, where R₁ and Y are as defined above, by treatment with anoxidizing reagent, such as Dess-Martin periodinane, in a solvent such asDCM, as shown in c. Compounds of Formula 10.3, where R₁ is as originallydefined and Y is Boc, can be prepared from compounds of Formula 10.2,where R₁ and Y are as defined above, by treatment with a fluorinatingreagent, such as Deoxo-Fluor®, in a solvent such as DCM, as shown in d.Compounds of Formula 10.4, where R₁ is as originally defined and Y isBoc, can be prepared from compounds of Formula 9.1, where R₁ and Y areas defined above, by treatment with a fluorinating reagent, such asDeoxo-Fluor®, in a solvent such as DCM or through halogenationconditions, such as treatment with perhalomethanes in the presence oftriphenylphosphine in DCM at a reduced temperature, such as 0° C., asshown in e. Compounds of Formula 10.5, where R₁ is as originally definedand Y is Boc, can be prepared from compounds of Formula 10.4, where R₁and Y are as defined above, by treatment with a reducing agent such astributyltin hydride in the presence of a radical initiator, such asazobisisobutyronitrile (AIBN), in a solvent such as toluene at anelevated temperature, for example 80° C., as shown in f. Compounds ofFormula 10.6, where R₁ is as originally defined and Y is Boc, can beprepared from compounds of Formula 9.1, where R₁ and Y are as definedabove, by treatment with a selenocyanate and a phosphine, such astributylphosphine, in a solvent such as THF at a temperature from about0° C. to about 23° C., as shown in g. Compounds of Formula 10.7, whereR₁ is as originally defined and Y is Boc, can be prepared from compoundsof Formula 10.6, where R₁ and Y are as defined above, by treatment withan oxidizing agent, such as hydrogen peroxide, in a solvent such as THF,as shown in h.

Compounds of Formulas 11.4 and 11.5 can be prepared through the methodsshown in Scheme 11, steps a-d. Compounds of Formula 11.4, where R₁ andR₂ are as originally defined, can be prepared from a variety ofprecursors, including, but not limited to, compounds of Formulas 11.0,11.1, 11.2, and 11.3, where R₁ and R₂ are as originally defined, and Yis Boc (11.0), X and Y are Boc (11.1), X is MOM and Y is Boc (11.2), andY is CBz (11.3) respectively. Treating compounds of Formulas 11.0-11.2with an acid, such as a 4.0 M hydrogen chloride (HCl) solution indioxane, in a solvent such as DCM affords the hydrochloride salt ofcompounds of Formula 11.4, which may be neutralized in situ in step d orneutralized prior to use to give the free amine, as shown in a.Additionally, compounds of Formula 11.4, where R₁ and R₂ are asoriginally defined, can be prepared from compounds of Formulas 11.0 and11.1, where R₁, R₂, X, and Y are as originally defined, by treatmentwith trimethylsilyl trifluoromethanesulfonate in the presence of a base,such 2,6-lutidine, in an aprotic solvent such as DCM, followed bytreatment with a protic solvent such as MeOH, as shown in b.Alternatively, compounds of Formula 11.4, where R₁ and R₂ are asoriginally defined, can be prepared from compounds of Formula 11.3,where R₁ and R₂ are as originally defined and Y is CBz, by treatmentwith hydrogen in the presence of a catalyst, such as 5% or 10% w/w Pd/C,in a solvent such as EtOAc, as shown in c. Compounds of Formula 11.5,where R₁ and R₂ are as originally defined, can be prepared fromcompounds of Formula 11.4, where R₁ and R₂ are as originally defined, bytreatment with 3-hydroxy-4-methoxypicolinic acid in the presence of anamine base, such as 4-methylmorpholine or triethylamine (TEA), and apeptide coupling reagent, such asO-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluroniumhexafluorophosphate (HATU) orbenzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate(PyBOP), in an aprotic solvent such as DCM, as shown in d.

Compounds of Formula 12.0, where R₁, R₂ and R₄ are as originallydefined, can be prepared by the method shown in Scheme 12. Compounds ofFormula 12.0 can be prepared from compounds of Formula 11.5, where R₁and R₂ are as originally defined, by treatment with the appropriatealkyl halide with or without a reagent such as sodium iodide (NaI) andan alkali carbonate base such as sodium carbonate (Na₂CO₃) or potassiumcarbonate (K₂CO₃) in a solvent such as acetone or by treatment with anacyl halide in the presence of an amine base, such as pyridine,triethylamine, DMAP, or mixtures thereof in an aprotic solvent such asDCM, as shown in a.

Compounds of Formula 13.0, where R₁ and R₄ are as originally defined andR₂ is cyclohexyl optionally substituted with one or multiple R₁₀,wherein R₁₀ is halo or alkyl, can be prepared by the method shown inScheme 13. Compounds of Formula 13.0 can be prepared from compounds ofFormula 12.0, where R₁ and R₄ are as originally defined and R₂ is aryloptionally substituted with one or multiple R₁₀, wherein R₁₀ is halo oralkyl, by treatment with hydrogen gas in the presence of a catalyst,such as rhodium on carbon (Rh/C), in a solvent such as THF at anelevated temperature such as 70° C., as shown in a.

The following examples are presented to illustrate the various aspectsof the compounds of the present disclosure and should not be construedas limitations to the claims.

EXAMPLES Example 1 Step 1: Preparation of(2S,3R,4S)-2-((4-methoxybenzyl)oxy)-7-methyl-4-vinyloctan-3-ol

Under a strict nitrogen atmosphere an oven-dried round-bottomed flaskwith a magnetic stir bar was charged withbis(1,5-cyclooctadiene)nickel(0) (0.297 grams (g), 1.080 millimole(mmol)) and tricyclohexylphosphine (0.379 g, 1.35 mmol). Anhydroustoluene (40 milliliters (mL)) followed by4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.34 ml, 57.5 mmol) and(E)-6-methylhepta-1,3-diene (11.9 g, 54.0 mmol), prepared according tothe procedure disclosed in Wang, Y.; West, F. G. Synthesis 2002, 99-103,were added to the flask and the reaction was allowed to stir at roomtemperature for 20 hours (h), as described in the diene hydroborationconditions reported in Ely, R. J.; Morken, J. P. J. Am. Chem. Soc. 2010,132, 2534-2535. To the mixture was added a solution of(S)-2-((4-methoxybenzyl)oxy)propanal (10.49 g, 54.0 mmol) in anhydroustoluene (5 mL) at −20° C. The reaction mixture was slowly warmed to roomtemperature and stirred at room temperature for 40 h, then quenched withMeOH and stirred for an additional 2 h. The crude mixture wasconcentrated under reduced pressure and purified by columnchromatography on silica gel (SiO₂; gradient, hexanes/ethyl acetate) toyield the title compound as a colorless oil (11.3 g, 69%): IR (neat)3467, 2925, 2868, 1513, 1247 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.27-7.22(m, 2H), 6.90-6.85 (m, 2H), 5.51-5.38 (m, 1H), 5.08-4.96 (m, 2H),4.52-4.40 (m, 2H), 3.80 (s, 3H), 3.66 (ddd, J=9.2, 3.1, 2.1 Hz, 1H),3.59-3.49 (m, 1H), 2.26-2.20 (m, 1H), 2.04-1.95 (m, 1H), 1.90-1.80 (m,1H), 1.59-1.43 (m, 1H), 1.29-1.14 (m, 2H), 1.13 (d, J=6.2 Hz, 3H),1.10-0.99 (m, 1H), 0.87 (d, J=6.4 Hz, 3H), 0.86 (d, J=6.4 Hz, 3H); ¹³CNMR (101 MHz, CDCl₃) δ 159.19, 138.56, 130.59, 129.22, 116.59, 113.82,75.89, 74.46, 70.11, 55.29, 47.18, 36.05, 28.57, 28.23, 22.98, 22.42,12.17; ESIMS m/z 329.2 ([M+Na]⁺).

Example 1 Step 2a: Preparation of1-methoxy-4-((((2S,3R,4S)-7-methyl-3-phenoxy-4-vinyloctan-2-yl)oxy)methyl)benzene

To a solution of(2S,3R,4S)-2-((4-methoxybenzyl)oxy)-7-methyl-4-vinyloctan-3-ol (2.0 g,6.53 mmol) in anhydrous toluene (30 mL) was addedbis(acetato-O)triphenylbismuth(V) (5.47 g, 9.79 mmol),N-cyclohexyl-N-methylcyclohexanamine (2.10 mL, 9.79 mmol) and anhydrousdiacetoxycopper (0.237 g, 1.305 mmol) at room temperature. The reactionwas heated at 43° C. for 5 h, filtered through a Celite® pad,concentrated and purified by column chromatography on SiO₂ (gradient,hexanes/ethyl acetate) to furnish the title product as a colorless oil(2.30 g, 92%): ¹H NMR (400 MHz, CDCl₃) δ 7.27-7.21 (m, 2H), 7.19-7.13(m, 2H), 7.03-6.97 (m, 2H), 6.94-6.88 (m, 1H), 6.86-6.81 (m, 2H),5.64-5.51 (m, 1H), 5.07-5.00 (m, 2H), 4.54-4.33 (m, 2H), 4.26 (dd,J=6.5, 4.7 Hz, 1H), 3.79 (s, 3H), 3.79-3.72 (m, 1H), 2.44-2.31 (m, 1H),1.74-1.61 (m, 1H), 1.52-1.38 (m, 1H), 1.34-1.25 (m, 1H), 1.23 (d, J=6.3Hz, 3H), 1.22-1.11 (m, 1H), 1.09-0.98 (m, 1H), 0.84 (d, J=6.8 Hz, 3H),0.82 (d, J=6.8 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 160.05, 159.04,139.48, 129.42, 129.32, 129.19, 121.56, 120.67, 116.46, 113.67, 83.41,75.26, 70.16, 55.26, 47.15, 36.47, 28.05, 27.64, 22.96, 22.34, 14.83;ESIMS m/z 405.3 ([M+Na]⁺).

Example 1 Step 2b: Preparation of1-((((2S,3R,4S)-3-(cyclopropylmethoxy)-7-methyl-4-vinyloctan-2-yl)oxy)methyl)-4-methoxybenzene

A solution of(2S,3R,4S)-2-((4-methoxybenzyl)oxy)-7-methyl-4-vinyloctan-3-ol (2.0 g,6.53 mmol) in anhydrous DMF (12 mL) was added at room temperature to asolution of NaH (NaH; 0.326 g, 8.16 mmol, 60% dispersion in mineral oil)in anhydrous DMF (12 ml). The reaction was stirred for 15 minutes (min)at room temperature, treated with (bromomethyl)cyclopropane (0.823 ml,8.48 mmol) at room temperature, and then was heated to 40° C. for andstirred for 6 h. The reaction was cooled to room temperature andadditional NaH (0.131 g, 3.27 mmol) and (bromomethyl)cyclopropane (0.317mL, 3.27 mmol) were added, and the reaction was heated at 45° C. for 4h. The reaction was again cooled to room temperature and a third batchof NaH (0.131 g, 3.27 mmol) followed by (bromomethyl)cyclopropane (0.317mL, 3.27 mmol) was added and the reaction was heated at 45° C. for 2 h.The reaction mixture was quenched with saturated aqueous ammoniumchloride (NH₄Cl) and the phases were separated. The aqueous phase wasextracted with diethyl ether (Et₂O), and the combined organic phaseswere washed with brine, dried over magnesium sulfate (MgSO₄),concentrated, and purified by column chromatography on SiO₂ (gradient,hexanes/ethyl acetate) to furnish the title product as a colorless oil(1.94 g, 82%): IR (neat) 2953, 2868, 1613, 1513, 1247, 1084 cm⁻¹; ¹H NMR(400 MHz, CDCl₃) δ 7.25-7.20 (m, 2H), 6.89-6.81 (m, 2H), 5.52 (dt,J=17.0, 10.0 Hz, 1H), 5.03-4.92 (m, 2H), 4.52-4.32 (m, 2H), 3.78 (s,3H), 3.65-3.56 (m, 2H), 3.34 (dd, J=10.0, 6.9 Hz, 1H), 3.28-3.22 (m,1H), 2.09 (tdd, J=10.1, 7.7, 3.1 Hz, 1H), 1.81-1.67 (m, 1H), 1.55-1.42(m, 1H), 1.28-1.13 (m, 2H), 1.19 (d, J=6.3 Hz, 3H), 1.13-0.95 (m, 2H),0.87 (d, J=6.4 Hz, 3H), 0.86 (d, J=6.8 Hz, 3H), 0.56-0.45 (m, 2H),0.25-0.14 (m, 2H); ESIMS m/z 383.4 ([M+Na]⁺).

Example 1 Step 2b: Preparation of1-((((2S,3R,4S)-3-isobutoxy-7-methyl-4-vinyloctan-2-yl)oxy)methyl)-4-methoxybenzene

A solution of(2S,3R,4S)-2-((4-methoxybenzyl)oxy)-7-methyl-4-vinyloctan-3-ol (2.0 g,6.53 mmol) in anhydrous DMF (15 mL) was added at room temperature to asolution of NaH (0.326 g, 8.16 mmol, 60% dispersion in mineral oil) inanhydrous DMF (6.0 mL). The reaction was stirred for 15 min at roomtemperature, then isobutyl 4-methylbenzenesulfonate (1.66 mL, 8.16 mmol)was added at room temperature and the reaction was heated at 50° C. andstirred for 1 h. The reaction was cooled down to room temperature andNaH (0.261 g, 6.53 mmol) followed by isobutyl 4-methylbenzenesulfonate(1.33 mL, 6.53 mmol) were added and heating continued for 2 h at 50° C.,after which the reaction was again cooled down to room temperature and athird batch of NaH (0.131 g, 3.27 mmol) and isobutyl4-methylbenzenesulfonate (0.67 mL, 3.27 mmol) were added and thereaction was heated at 50° C. for 7 h. The reaction mixture was quenchedwith saturated NH₄Cl and the phases were separated. The aqueous phasewas extracted with Et₂O, and the combined organic phases were washedwith brine, dried over MgSO₄, concentrated, and purified by columnchromatography on SiO₂ (gradient, hexanes/ethyl acetate) to furnish thetitle product as a colorless oil (2.05 g, 87%): ¹H NMR (400 MHz, CDCl₃)δ 7.29-7.21 (m, 2H), 6.90-6.83 (m, 2H), 5.61-5.49 (m, 1H), 5.04-4.89 (m,2H), 4.53-4.33 (m, 2H), 3.80 (s, 3H), 3.64-3.51 (m, 2H), 3.28-3.16 (m,2H), 2.15-2.02 (m, 1H), 1.90-1.77 (m, 1H), 1.76-1.60 (m, 1H), 1.54-1.41(m, 1H), 1.28-1.11 (m, 2H), 1.17 (d, J=6.3 Hz, 3H), 1.08-0.96 (m, 1H),0.95-0.88 (m, 6H), 0.86 (d, J=6.4 Hz, 3H), 0.85 (d, J=6.4 Hz, 3H); ¹³CNMR (101 MHz, CDCl₃) δ 158.97, 140.43, 131.09, 129.06, 115.66, 113.67,84.26, 79.58, 76.41, 70.05, 55.26, 47.38, 36.46, 29.13, 28.21, 27.85,22.91, 22.47, 19.66, 19.55, 14.25; ESIMS m/z 385.4 ([M+Na]⁺).

Example 1 Step 2b: Preparation of1-((2S,3R,4S)-3-(benzyloxy)-4-((4-methoxy-benzyl)oxy)-2-vinylpentyl)-2,4-difluorobenzene

An oven-dried 100 mL Schlenk flask was cooled under nitrogen and wasthen charged with NaH (60% dispersion in mineral oil, 1.24 g, 31.0 mmol)and anhydrous DMF (50 mL). A solution of(2S,3R,4S)-4-(2,4-difluorobenzyl)-2-((4-methoxybenzyl)oxy)hex-5-en-3-ol(8.06 g, 22.2 mmol) in anhydrous DMF (10 mL) was added via canula over aperiod of 6 min followed by an anhydrous DMF rinse (5 mL) of the sourceflask and needle. Gas evolution was observed, and the resulting whitesuspension was stirred at room temperature for 90 min, at which pointthe reaction color had turned red. Benzyl bromide (4.23 mL, 35.6 mmol)was added and the reaction was heated to 40° C. After stirring for 3hours, the heat source was removed and the reaction was cooled to roomtemperature. Saturated aqueous NH₄Cl solution (20 mL) was added, and themixture was allowed to stir for 30 min, at which point gas evolution hadceased. The crude mixture was then diluted with H₂O (50 mL) andextracted with Et₂O (100 mL×3). The combined organic extracts werewashed with saturated aqueous NH₄Cl solution (100 mL), dried overanhydrous MgSO₄, filtered, concentrated, and the residue was purified bycolumn chromatography on SiO₂ (0%→10% methyl tert-butylether(MTBE)/hexane gradient) to furnish the title product as white solid (90%Pure, 8.47 g, 84%): mp 141-144° C.; ¹H NMR (400 MHz, CDCl₃) δ 7.41-7.30(m, 4H), 7.30-7.24 (m, 3H), 7.05-6.96 (m, 1H), 6.90-6.84 (m, 2H),6.76-6.67 (m, 2H), 5.57 (dddd, J=17.1, 10.3, 9.0, 1.3 Hz, 1H), 4.88 (dd,J=10.2, 1.9 Hz, 1H), 4.87 (d, J=11.4 Hz, 1H), 4.72 (ddd, J=17.2, 1.8,0.5 Hz, 1H), 4.63 (d, J=11.4 Hz, 1H), 4.53 (d, J=11.3 Hz, 1H), 4.40 (d,J=11.3 Hz, 1H), 3.79 (s, 3H), 3.70 (qd, J=6.2, 3.8 Hz, 1H), 3.52 (dd,J=6.9, 3.9 Hz, 1H), 3.09 (d, J=10.4 Hz, 1H), 2.59-2.44 (m, 2H), 1.25 (d,J=6.3 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 161.24 (dd, J=245.7, 11.9 Hz),161.09 (dd, J=247.0, 11.6 Hz), 159.11, 138.90, 138.24, 132.05 (dd,J=9.4, 6.7 Hz), 130.92, 129.17, 128.33, 127.97, 127.53, 123.45 (dd,J=15.9, 3.7 Hz), 116.95, 113.78, 110.59 (dd, J=20.8, 3.7 Hz), 103.33(dd, J=26.5, 25.0 Hz), 83.67, 76.56, 74.18, 70.41, 55.28, 47.98, 29.75,14.24; ¹⁹F NMR (376 MHz, CDCl₃) δ−113.06 (d, J=6.8 Hz), −113.95 (d,J=6.4 Hz); ESIMS: m/z 475 ([M+Na]⁺).

Example 1 Step 2b: Preparation of1-((((2S,3R,4S)-4-benzyl-3-(2-methoxyethoxy)-hex-5-en-2-yl)oxy)methyl)-4-methoxybenzene

To a suspension of NaH (0.088 g, 3.68 mmol) in DMF (10 mL) was addeddropwise a solution of(2S,3R,4S)-4-benzyl-2-((4-methoxybenzyl)oxy)hex-5-en-3-ol (1 g, 3.06mmol) in DMF (5 mL). The mixture was stirred at room temperature for 20min and then 1-bromo-2-methoxyethane (0.852 g, 6.13 mmol) was added. Thereaction mixture was heated to 60° C. for 5 h. The reaction was cooledto room temperature and another portion of NaH (0.088 g, 3.68 mmol) and1-bromo-2-methoxyethane (0.852 g, 6.13 mmol) were added, and thereaction mixture was heated to 60° C. and stirred overnight. Thereaction mixture was quenched with saturated NH₄Cl and the phases wereseparated. The aqueous phase was extracted with EtOAc (2×40 mL), and thecombined organic phases were dried over MgSO₄, concentrated, andpurified by column chromatography on SiO₂ (EtOAc/hexanes) to furnish thetitle product as as colorless oil (0.730 g, 62%): ¹H NMR (400 MHz,CDCl₃) δ 7.30-7.06 (m, 7H), 6.86 (dd, J=8.6, 0.9 Hz, 2H), 5.68-5.47 (m,1H), 4.95-4.69 (m, 2H), 4.60-4.26 (m, 2H), 4.04-3.91 (m, 1H), 3.79 (s,3H), 3.73-3.69 (m, 1H), 3.68-3.60 (m, 1H), 3.59-3.53 (m, 2H), 3.39 (d,J=0.8 Hz, 3H), 3.38-3.36 (m, 1H), 3.15 (d, J=10.4 Hz, 1H), 2.70-2.42 (m,2H), 1.30-1.17 (m, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 159.05, 140.67,138.83, 130.95, 129.56, 129.11, 127.92, 125.60, 116.61, 113.74, 84.59,76.46, 72.41, 71.76, 70.26, 58.96, 55.28, 48.55, 36.96, 14.01; ESIMS m/z407.2 ([M+Na]⁺).

Example 1 Step 2c: Preparation oftriisopropyl(((2S,3R,4S)-2-((4-methoxybenzyl)-oxy)-7-methyl-4-vinyloctan-3-yl)oxy)silane

To an ice-cooled solution of(2S,3R,4S)-2-((4-methoxybenzyl)oxy)-7-methyl-4-vinyloctan-3-ol (3.70 g,12.07 mmol) in anhydrous CH₂Cl₂ (60.4 ml) were added2,6-dimethylpyridine (1.97 ml, 16.9 mmol) and triisopropylsilyltrifluoromethanesulfonate (3.89 ml, 14.5 mmol), and the mixture wasallowed to warm to room temperature while stirring overnight. Thereaction mixture was poured into saturated aqueous sodium bicarbonate(NaHCO₃) solution and mixed thoroughly. The phases were separated andthe aqueous phase was extracted with CH₂Cl₂, and the combined organicphases were washed with brine, dried over MgSO₄, concentrated, andpurified by column chromatography on SiO₂ (gradient, hexanes/ethylacetate) to furnish the title product as as a colorless oil (4.76 g,85%): ¹H NMR (400 MHz, CDCl₃) δ 7.26-7.19 (m, 2H), 6.88-6.81 (m, 2H),5.63-5.50 (m, 1H), 5.05-4.89 (m, 2H), 4.51-4.29 (m, 2H), 3.84 (dd,J=6.6, 3.0 Hz, 1H), 3.79 (s, 3H), 3.55-3.46 (m, 1H), 2.11-1.98 (m, 1H),1.75-1.61 (m, 1H), 1.56-1.41 (m, 1H), 1.24-1.17 (m, 1H), 1.15 (d, J=6.2Hz, 3H), 1.13-0.97 (m, 20H), 0.85 (d, J=6.8 Hz, 3H), 0.84 (d, J=6.4 Hz,3H); ¹³C NMR (101 MHz, CDCl₃) δ 158.88, 139.86, 131.19, 129.19, 115.64,113.50, 78.34, 76.39, 70.08, 55.24, 49.46, 36.94, 28.35, 28.23, 22.83,22.51, 18.43, 18.41, 13.71, 13.18; ESIMS m/z 485.4 ([M+Na]⁺).

Example 1 Step 3: Preparation of (6R,7R,8S,Z)-benzyl2-((tert-butoxycarbonyl)amino)-7-(cyclopropylmethoxy)-6-(4-fluorobenzyl)-8-((4-methoxybenzyl)-oxy)non-2-enoate

A 0.5 M solution of 9-borabicyclo[3.3.1]nonane in anhydrous THF (7.0 mL,3.50 mmol) was added to a solution of1-((2S,3R,4S)-3-(cyclopropylmethoxy)-4-((4-methoxybenzyl)oxy)-2-vinylpentyl)-4-fluorobenzene(960 milligrams (mg), 2.409 mmol) in anhydrous THF (5 mL) at 0° C. Theresulting solution was warmed to room temperature and stirred for 1 h,then heated to 50° C. for 2 h. The reaction was cooled to roomtemperature, a solution of K₃PO₄ (3 M aqueous, 1.61 mL, 4.82 mmol) wasadded, and the reaction was stirred for 15 min at room temperature. Tothe mixture was added a solution of (Z)-benzyl3-bromo-2-((tert-butoxycarbonyl)amino)acrylate (870 mg, 2.44 mmol),prepared using a similar procedure to that disclosed in Singh, J. et al.Org. Lett. 2003, 5, 3155-3158, in degassed DMF (2 mL) and PdCl₂(dppf)(88.0 mg, 0.120 mmol). The reaction was heated overnight at 60° C.,cooled, diluted with Et₂O, and washed with saturated aqueous NaHCO₃. Thephases were separated and the aqueous phase was extracted with Et₂O. Thecombined organic phases were washed with saturated aqueous NH₄Cl andwater, dried over MgSO₄, concentrated, and purified by columnchromatography on SiO₂ (gradient, hexanes/ethyl acetate) to furnish thetitle product as a pale yellow oil (1.43 g, 88%): ¹H NMR (400 MHz,CDCl₃) δ 7.38-7.26 (m, 5H), 7.26-7.19 (m, 2H), 6.97-6.89 (m, 2H),6.88-6.78 (m, 4H), 6.39 (t, J=7.2 Hz, 1H), 6.29 (s, 1H), 5.24-5.10 (m,2H), 4.61-4.25 (m, 2H), 3.73 (s, 3H), 3.64-3.53 (m, 1H), 3.45-3.31 (m,2H), 3.22 (dd, J=7.2, 2.8 Hz, 1H), 2.79 (dd, J=14.0, 4.8 Hz, 1H), 2.37(dd, J=14.0, 9.5 Hz, 1H), 2.25-2.08 (m, 2H), 1.92-1.79 (m, 1H),1.57-1.43 (m, 1H), 1.43 (s, 9H), 1.39-1.28 (m, 1H), 1.28 (d, J=6.0 Hz,3H), 1.09-0.96 (m, 1H), 0.53-0.44 (m, 2H), 0.21-0.13 (m, 2H); ¹³C NMR(101 MHz, CDCl₃) δ 164.48, 160.91 (d, J=243.2 Hz), 158.99, 153.40,136.94 (d, J=3.2 Hz), 136.82, 135.55, 130.26, 130.24 (d, J=7.7 Hz),129.39, 128.31, 128.04, 128.00, 126.23, 114.62 (d, J=20.9 Hz), 113.58,82.58, 80.01, 76.69, 74.41, 69.70, 66.72, 54.94, 40.81, 34.83, 28.49,27.99, 25.75, 16.00, 11.01, 2.86, 2.78; ¹⁹F NMR (376 MHz, CDCl₃)δ−117.70; ESIMS m/z 676.4 ([M+H]⁺).

Example 1 Step 4:(2S,6R,7R,8S)-methyl-2-((tert-butoxycarbonyl)amino)-6-(4-methoxybenzyl)-8-((4-methoxybenzyl)oxy)-7-((triisopropylsilyl)oxy)nonanoate

The title compound was prepared using a procedure adapted from Jones etal. Tetrahedron Lett. 1999, 40, 1211-1214. A high pressure reactor wascharged with (6R,7R,8S,Z)-methyl7-(benzyloxy)-2-((tert-butoxycarbonyl)amino)-8-((4-methoxybenzyl)oxy)-6-(4-methylbenzyl)non-2-enoate(2.72 g, 3.82 mmol) and anhydrous MeOH (20 mL) and the solution wassparged with nitrogen using a needle for 10 min. To the solution wasadded(+)-1,2-bis((2S,5S)-2,5-diethylphospholano)benzene-(cyclooctadiene)rhodium(I)trifluoromethanesulfonate (28 mg, 0.038 mmol) and the reactor wassealed, pressurized with H₂ (200 psi) and stirred at room temperaturefor 3 h. The pressure was released and the crude reaction mixture wasfiltered through a pad of Celite®, concentrated, and purified by columnchromatography on SiO₂ (0→100% EtOAc/hexanes gradient) to furnish thetitle product as a colorless oil (2.73 g, 100%): IR (neat) 3377, 2941,2865, 1744, 1715, 1511, 1245, 1164 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ7.31-7.22 (m, 2H), 7.01 (d, J=8.5 Hz, 2H), 6.87 (d, J=8.6 Hz, 2H), 6.77(d, J=8.6 Hz, 2H), 4.90 (d, J=8.5 Hz, 1H), 4.51 (d, J=11.2 Hz, 1H), 4.33(d, J=11.3 Hz, 1H), 4.25 (q, J=7.2 Hz, 1H), 3.81 (s, 3H), 3.78 (s, 3H),3.70 (s, 3H), 3.63-3.52 (m, 1H), 2.77 (dd, J=13.8, 7.2 Hz, 1H), 2.43(dd, J=13.8, 7.4 Hz, 1H), 1.78 (d, J=7.7 Hz, 1H), 1.70 (s, 1H), 1.52 (d,J=10.7 Hz, 2H), 1.44 (s, 9H), 1.35-1.07 (m, 7H), 1.07-0.93 (m, 21H); ¹³CNMR (101 MHz, CDCl₃) δ 173.40, 158.94, 157.67, 155.35, 133.91, 131.04,130.15, 129.21, 113.63, 113.58, 79.80, 76.44, 76.36, 70.18, 55.29,55.26, 53.37, 52.16, 45.89, 36.12, 33.12, 29.50, 28.32, 23.81, 18.27,16.23, 13.02; HRMS-ESI (m/z) ([M]⁺) calcd for C₄₀H₆₅NO₈Si, 715.448.found, 715.4479.

Example 1 Step 5a: Preparation of (2S,6R,7R,8S)-methyl2-((tert-butoxycarbonyl)-amino)-8-hydroxy-7-isobutoxy-6-(2-(methylthio)ethyl)nonanoate

To a mixture of (2S,6R,7R,8S)-methyl2-((tert-butoxycarbonyl)amino)-7-isobutoxy-8-((4-methoxybenzyl)oxy)-6-(2-(methylthio)ethyl)nonanoate(536 mg, 0.941 mmol) and 0.85 mL H₂O in CH₂Cl₂ (9.4 mL) at 0° C.(icewater bath) was added DDQ (214 mg, 0.941 mmol). The resulting darkmixture was stirred at 0° C. for 3 h, then another portion of DDQ (41mg, 0.180 mmol) were added and the reaction was stirred for 1 h. Thereaction was quenched with sodium hydroxide (NaOH; 1.3 ml of 1M aqueous,1.3 mmol) and stirred for 10 min. The reaction was then diluted with H₂O(20 mL) and extracted with CH₂Cl₂ (3×20 mL). The combined organicextracts were dried over Na₂SO₄, filtered, and concentrated to provide ared oil which was purified by column chromatography on SiO₂ (5→35%acetone/hexanes gradient) to furnish the title product as a clear,colorless oil (353 mg, 83%): ¹H NMR (400 MHz, CDCl₃) δ 5.02 (d, J=8.0Hz, 1H), 4.31 (d, J=5.2 Hz, 1H), 3.95-3.83 (m, 1H), 3.74 (d, J=1.6 Hz,3H), 3.36 (dd, J=8.5, 6.3 Hz, 1H), 3.22 (dd, J=8.5, 6.6 Hz, 1H), 3.05(dd, J=5.6, 3.9 Hz, 1H), 2.58 (ddd, J=14.0, 8.7, 5.3 Hz, 1H), 2.47 (ddd,J=12.8, 8.3, 7.4 Hz, 1H), 2.10 (s, 3H), 1.96-1.68 (m, 4H), 1.68-1.49 (m,3H), 1.45 (s, 9H), 1.39 (s, 4H), 1.21 (d, J=6.3 Hz, 3H), 0.91 (dd,J=6.7, 1.9 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 173.36, 155.36, 84.83,79.93, 79.24, 68.10, 53.20, 52.27, 38.01, 33.20, 33.05, 32.76, 30.90,29.21, 28.83, 28.33, 22.83, 19.52, 19.46, 19.11, 15.43; ESIMS m/z 450.4([M+H]+), 472.4 ([M+Na]⁺).

Example 1 Step 5b: Preparation of(2S,6R,7R,8S)-2-((tert-butoxycarbonyl)amino)-8-hydroxy-6-(4-methylbenzyl)-7-phenoxynonanoicacid

A 25 mL screw top vial was charged with (2S,6R,7R,8S)-benzyl8-(benzyloxy)-2-((tert-butoxycarbonyl)amino)-6-(4-methylbenzyl)-7-phenoxynonanoate(741 mg, 1.11 mmol), EtOAc (10 mL), and 10% Pd/C (61 mg, 0.057 mmol).The vial was sealed with a septum-cap, and the reaction was brieflydegassed under high vacuum, and then repressurized under about 1atmosphere of H₂ (balloon pressure). This process was repeated 2×, andthe reaction was stirred at room temperature under balloon pressure ofhydrogen. After stirring for 19 h, the solids were removed by filtrationthrough a pad of Celite®, rinsing with excess EtOAc. The filtrate wasconcentrated and then dried under high vacuum to afford the titlecompound as a white solid (516 mg, 91%): mp 48-51° C.; ¹H NMR (400 MHz,CDCl₃) δ 7.30-7.17 (m, 2H), 7.09 (s, 4H), 6.97-6.83 (m, 3H), 6.69-6.02(m, 2H), 5.00 (d, J=8.3 Hz, 1H), 4.33-3.96 (m, 3H), 3.03 (dd, J=13.8,5.3 Hz, 1H), 2.49 (dd, J=13.9, 8.9 Hz, 1H), 2.33 (s, 3H), 2.19-2.08 (m,1H), 1.78-1.62 (m, 1H), 1.59-1.15 (m, 17H); ¹³C NMR (101 MHz, CDCl₃) δ176.73, 159.43, 155.73, 138.03, 135.33, 129.57, 129.10, 129.06, 120.88,115.85, 82.16, 80.24, 68.15, 53.26, 41.47, 35.46, 32.45, 29.53, 28.35,22.51, 21.05, 20.01; ESIMS: m/z 486 ([M+H]⁺).

Example 1 Step 5b: Preparation of(2S,6R,7R,8S)-2-((tert-butoxycarbonyl)amino)-8-hydroxy-6-(4-methoxybenzyl)-7-(triisopropylsilyl)oxy)nonanoicacid

A high pressure reactor was charged with Pd/C (212 mg, 0.199 mmol) and asolution of(2S,6R,7R,8S)-benzyl-2-((tert-butoxycarbonyl)amino)-8-hydroxy-6-(4-methoxybenzyl)-7-((triisopropylsilyl)oxy)nonanoate(2.02 g, 3.01 mmol) in THF (10 mL). The flask was pressurized to 500 psiand stirred for 2 days (d). The reaction mixture was filtered through apad of Celite® and concentrated to give the title compound as a stickysemi solid (1.730 g, 99%): IR (neat) 3337, 2941, 2865, 1714, 1511, 1462,1245, 1165 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.13-6.90 (m, 2H), 6.88-6.67(m, 2H), 4.87 (d, J=8.0 Hz, 1H), 4.22 (s, 1H), 3.96 (qd, J=6.4, 4.0 Hz,1H), 3.79 (s, 3H), 3.76-3.62 (m, 1H), 2.93 (dd, J=14.0, 5.9 Hz, 1H),2.44 (dd, J=13.9, 8.7 Hz, 1H), 1.92-1.65 (m, 2H), 1.62-1.48 (m, 2H),1.44 (s, 9H), 1.34-1.14 (m, 6H), 1.14-0.71 (m, 21H); ¹³C NMR (101 MHz,CDCl₃) δ 175.71, 157.74, 155.72, 133.62, 130.02, 113.74, 70.38, 60.42,55.27, 53.21, 43.79, 35.95, 32.41, 29.79, 28.30, 23.72, 19.11, 18.28,14.20, 13.03; HRMS-ESI (m/z) ([M]⁺) calcd for C₃₁H₅₅NO₇Si, 581.3748.found, 581.3744.

Example 1 Step 5b: Preparation of(2S,6R)-2-((tert-butoxycarbonyl)amino)-6-((1R,2S)-2-hydroxy-1-((triisopropylsilyl)oxy)propyl)-9-methyldecanoicacid

(2S,6R)-2-((tert-Butoxycarbonyl)amino)-6-((1R,2S)-2-((4-methoxybenzyl)oxy)-1-((triisopropylsilyl)oxy)propyl)-9-methyldecanoicacid (8.55 g, 13.1 mmol) was dissolved in THF (40 ml) in a high pressurereactor with a stir bar. To the resulting solution was added 5% Pd/C(1.40 g, 0.656 mmol) was added, the reactor was sealed and purged withH₂ (4×), and then charged to 600 psi with H₂ at room temperature. Thereactor was heated to 50° C. for 12 h and then stirred at roomtemperature overnight. The reaction mixture was filtered through a padof Celite® and concentrated to yield the title compound as a colorlessoil contaminated with 20% p-methoxytoluene (7.76 g, 89: ¹H NMR (400 MHz,CDCl₃) δ 5.05-4.92 (m, 1H), 4.37-4.22 (m, 1H), 3.89 (qd, J=6.4, 3.5 Hz,1H), 3.83-3.78 (m, 1H), 1.93-1.77 (m, 2H), 1.74-1.45 (m, 5H), 1.45 (s,9H), 1.45-1.19 (m, 2H), 1.19 (d, J=5.1 Hz, 3H), 1.14-1.02 (m, 24H), 0.87(d, J=6.6 Hz, 6H); ESIMS m/z 554.5 ([M+Na]⁺).

Example 1 Step 5c: Preparation of(2S,6R,7R,8S)-7-(benzyloxy)-2-((tert-butoxy-carbonyl)amino)-6-(2,4-difluorobenzyl)-8-hydroxynonanoicacid

A 250 mL round bottom flask was charged with (2S,6R,7R,8S)-benzyl7-(benzyloxy)-2-((tert-butoxycarbonyl)amino)-6-(2,4-difluorobenzyl)-8-hydroxynonanoate(2.10 g, 3.43 mmol), THF (24 mL) and H₂O (6 mL). LiOH.H₂O (153 mg, 3.64mmol) was added, and the resulting mixture was allowed to stir at roomtemperature. After stirring for 2.5 h, the reaction mixture was heatedto 50° C. and was stirred for an additional 17 h at that temperature.Additional portions of water (3 mL) and LiOH.H₂O (152 mg, 3.62 mmol)were added and the reaction was stirred at room temperature for 4.5 h.The reaction mixture was diluted with 1.0 M aqueous HCl (50 mL) andextracted with EtOAc (3×50 mL). The combined organic extracts werewashed with saturated aqueous sodium chloride solution (NaCl, brine; 50mL), dried over anhydrous MgSO₄, filtered, concentrated, and dried underhigh vacuum to obtain the title compound as a colorless oil contaminatedwith 10% BnOH (1.55 g, 87%): ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.26 (m,5H), 7.15-7.05 (m, 1H), 6.82-6.69 (m, 2H), 5.03 (d, J=8.3 Hz, 1H), 4.64(d, J=11.5 Hz, 1H), 4.55 (d, J=11.6 Hz, 1H), 4.20 (q, J=7.4 Hz, 1H),4.03 (p, J=6.2 Hz, 1H), 3.37-3.24 (m, 1H), 2.99 (dd, J=14.0, 4.6 Hz,1H), 2.51 (dd, J=14.0, 9.9 Hz, 1H), 2.01-1.90 (m, 1H), 1.75-1.60 (m,1H), 1.56-1.15 (m, 17H); ¹³C NMR (101 MHz, CDCl₃) δ 176.51, 161.26 (dd,J=246.7, 12.7 Hz), 161.07 (dd, J=247.1, 12.0 Hz), 155.60, 138.35, 131.98(dd, J=9.3, 6.9 Hz), 128.37, 127.77, 126.97, 124.00 (dd, J=15.8, 3.8Hz), 110.83 (dd, J=20.8, 3.6 Hz), 104.38 102.95 (m), 83.36, 80.11,73.75, 68.11, 53.17, 39.82, 32.49, 29.71, 28.85, 28.25, 22.55, 19.22;19F NMR (376 MHz, CDCl3) δ−113.45 (d, J=7.0 Hz), −113.63 (d, J=6.7 Hz);ESIMS: m/z 522 ([M+H]⁺).

Example 1 Step 5c: Preparation of(2S,6R)-2-((tert-butoxycarbonyl)amino)-6-((1R,2S)-2-((4-methoxybenzyl)oxy)-1-((triisopropylsilyl)oxy)propyl)-9-methyldecanoicacid

To a solution of (2S,6R)-methyl2-((tert-butoxycarbonyl)amino)-6-((1R,2S)-2-((4-methoxybenzyl)oxy)-1-((triisopropylsilyl)oxy)propyl)-9-methyldecanoate(8.76 g, 13.2 mmol) in a mixture of THF and H₂O (125 mL/62.5 mL) wasadded LiOH (2.047 g, 85.0 mmol) and the resulting mixture was stirredfor 24 h at 40° C. and then for another 24 h at room temperature. Thereaction mixture was diluted with EtOAc and washed with 1.0 M aqueousHCl. The phases were separated and the aqueous phase was extracted withEtOAc. The combined organic phase was washed with brine, dried overMgSO₄, and concentrated to furnish the title compound as a pale yellowoil (8.55 g, 100%): IR (neat) 2943, 2866, 1715, 1513, 1392, 1247, 1162,1038 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.26-7.20 (m, 2H), 6.88-6.82 (m,2H), 4.96-4.83 (m, 1H), 4.51-4.31 (m, 2H), 4.31-4.20 (m, 1H), 3.88 (t,J=3.8 Hz, 1H), 3.80 (s, 3H), 3.52-3.43 (m, 1H), 1.91-1.72 (m, 2H),1.68-1.46 (m, 5H), 1.45 (s, 9H), 1.44-1.19 (m, 2H), 1.18 (d, J=6.2 Hz,3H), 1.18-0.98 (m, 24H), 0.86-0.80 (m, 6H); ESIMS m/z 674.6 ([M+Na]⁺).

Example 1 Step 5c: Preparation of(2S,6R,7R,8S)-2-((tert-butoxycarbonyl)amino)-8-hydroxy-7-isobutoxy-6-(2-(methylthio)ethyl)nonanoicacid

To a mixture of (2S,6R,7R,8S)-methyl2-((tert-butoxycarbonyl)amino)-8-hydroxy-7-isobutoxy-6-(2-(methylthio)ethyl)nonanoate(326 mg, 0.725 mmol) in THF (2.4 ml) and H₂O (1.2 ml) was added LiOH.H₂O(91 mg, 2.2 mmol). The resulting mixture was stirred at room temperaturefor 3 h, quenched with 2N HCl (3 mL), diluted with H₂O (20 mL), andextracted with EtOAc (3×20 mL). The organic extracts were combined,dried over Na₂SO₄, filtered, and concentrated to provide the titlecompound as a sticky colorless oil (307 mg, 97%): ¹H NMR (400 MHz,CDCl₃) δ 5.05 (d, J=7.3 Hz, 1H), 4.31 (s, 1H), 3.88 (p, J=6.3 Hz, 1H),3.36 (dd, J=8.5, 6.3 Hz, 1H), 3.23 (dd, J=8.6, 6.6 Hz, 1H), 3.07 (dd,J=5.7, 3.9 Hz, 1H), 2.59 (ddd, J=13.9, 8.6, 5.3 Hz, 1H), 2.48 (dt,J=12.8, 7.5 Hz, 1H), 2.10 (s, 3H), 1.84 (tt, J=13.2, 7.1 Hz, 3H), 1.781.62 (m, 2H), 1.55 (dd, J=13.6, 5.8 Hz, 1H), 1.46 (s, 12H), 1.22 (d,J=6.3 Hz, 3H), 0.91 (dd, J=6.7, 2.0 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ155.81, 99.99, 84.81, 79.35, 68.26, 38.01, 32.80, 30.94, 29.22, 28.80,28.32, 22.88, 19.51, 19.46, 19.13, 15.44; ESIMS m/z 436.3 ([M+H]⁺),458.3 ([M+Na]⁺).

Example 1 Step 6: Preparation of tert-butyl((3S,7R,8R,9S)-7-isopentyl-9-methyl-2-oxo-8-((triisopropylsilyl)oxy)oxonan-3-yl)carbamate

A solution of(2S,6R)-2-((tert-butoxycarbonyl)amino)-6-((1R,2S)-2-hydroxy-1-((triisopropylsilyl)oxy)propyl)-9-methyldecanoicacid (7.76 g, 13.1 mmol) in anhydrous CH₂Cl₂ (500 mL) was added to asolution of MNBA (9.04 g, 26.3 mmol) and DMAP (12.8 g, 105.0 mmol) inanhydrous CH₂Cl₂ (2.5 L) at room temperature over the course of 4 h.After the addition was complete, the reaction was stirred for 12 h atroom temperature, concentrated and purified by column chromatography onSiO₂ (gradient, hexanes/ethyl acetate) to furnish the title product as asticky pale yellow solid (3.98 g, 59%): ¹H NMR (400 MHz, CDCl₃) δ 5.14(d, J=8.2 Hz, 1H), 4.90-4.78 (m, 1H), 4.20-4.09 (m, 1H), 3.61 (t, J=7.6Hz, 1H), 2.26-2.10 (m, 1H), 1.79-1.65 (m, 1H), 1.65-1.40 (m, 3H), 1.44(s, 9H), 1.37 (d, J=6.5 Hz, 3H), 1.32-0.97 (m, 28H), 0.884 (d, J=6.7 Hz,3H), 0.878 (d, J=6.7 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 173.12, 154.92,79.62, 78.59, 75.82, 60.33, 53.07, 45.68, 36.92, 34.17, 28.64, 28.58,28.31, 27.27, 22.82, 22.49, 18.95, 18.86, 18.38, 18.33, 13.75; ESIMS m/z536.5 ([M+Na]⁺).

Example 2 Step 1a-1: Preparation of tert-butyl((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-((triisopropylsilyl)oxy)oxonan-3-yl)(methoxymethyl)carbamate

A 4 mL vial was charged with tert-butyl((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-((triisopropylsilyl)oxy)oxonan-3-yl)carbamate(42.0 mg, 0.074 mmol), paraformaldehyde (3.13 mg, 0.104 mmol) and CH₂Cl₂(0.5 mL), then cooled to 0° C. under N₂. Chlorotrimethylsilane (0.026mL, 0.201 mmol) was added to the reaction mixture, which was stirred for45 min, then quenched by the addition of 9:1 MeOH/Et₃N (0.5 mL). Themixture was warmed to room temperature and stirred overnight. Thereaction was diluted with H₂O (2 mL) and passed through a phaseseparator cartridge. An additional portion of CH₂Cl₂ (2 mL) was passedthrough the separator and the combined organics were concentrated toafford the title compound as a colorless oil: IR (neat) 3445, 2942,2866, 1747, 1706, 1512, 1464, 1367, 1247, 1175 cm⁻¹; ¹H NMR (400 MHz,CDCl₃) δ 7.00 (d, J=8.6 Hz, 2H), 6.76 (d, J=8.6 Hz, 2H), 5.05-4.45 (m,3H), 4.23-4.03 (m, 1H), 3.72 (s, 4H), 3.68 (t, J=8.2 Hz, 1H), 3.23 (d,J=13.1 Hz, 3H), 3.09-2.97 (m, 2H), 2.23 (td, J=12.9, 5.4 Hz, 1H),2.01-1.96 (m, 1H), 1.73 (d, J=9.8 Hz, 1H), 1.42-1.32 (m, 3H), 1.13-1.05(m, 21H), 0.99 (d, J=0.8 Hz, 9H), 0.91-0.77 (m, 3H); ¹³C NMR (101 MHz,CDCl₃) δ 155.89, 127.66, 111.86, 53.32, 45.75, 43.84, 35.14, 34.42,26.38, 26.30, 24.77, 22.70, 17.65, 16.86, 16.56, 16.46, 15.89, 15.76,12.07, 10.72, 10.35, 6.69, 0.00, −1.94 (Note: Peaks missing, likely dueto rotamers); HRMS-ESI (m/z) ([M]⁺) calcd for C₃₃H₅₇NO₇Si, 607.3897.found, 607.3904.

Example 2 Step 1a-2: Preparation of tert-butyl((3S,7R,8R,9S)-8-hydroxy-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate

To a round bottom flask were added tert-butyl((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-((triisopropylsilyl)oxy)oxonan-3-yl)(methoxymethyl)carbamate(1.61 g, 2.65 mmol), THF (26.5 ml) and TBAF (1.0 M, 5.30 ml, 5.30 mmol)at room temperature and an exotherm noted. The reaction was stirred atroom temperature until thin layer chromatography (TLC) showed completeconsumption of starting material. After approximately 2 h, the reactionwas quenched by the addition of NaHCO₃ and extracted with EtOAc (3×).The combined organic extracts were washed with brine, dried over MgSO4,concentrated, and purified by column chromatography on SiO₂ (0→10%,hold, 10→20%, hold, 20→50% hold EtOAc/hexanes gradient) to furnish thetitle product as a colorless oil (703 mg, 59%): IR (neat) 3479, 2976,2936, 1744, 1700, 1512, 1368, 1297, 1246, 1175 cm⁻¹; ¹H NMR (400 MHz,CDCl₃) δ 7.15-7.06 (m, 2H), 6.87-6.79 (m, 2H), 4.96-4.87 (m, 1H),4.85-4.73 (m, 2H), 4.61-4.49 (m, 1H), 4.23-4.18 (m, 1H), 3.79 (s, 3H),3.51 (td, J=8.8, 5.8 Hz, 1H), 3.32 (d, J=12.9 Hz, 3H), 3.01 (dd, J=13.6,4.9 Hz, 1H), 2.44 (dd, J=16.2, 7.3 Hz, 1H), 2.07 (d, J=16.5 Hz, 1H),1.69 (s, 2H), 1.63-1.49 (m, 3H), 1.44 (d, J=5.9 Hz, 9H), 1.40 (d, J=6.3Hz, 3H), 0.94 (s, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 173.45, 158.00,129.72, 113.97, 76.28, 55.25, 37.08, 28.24, 27.29, 19.43, 18.18 (Note:Peaks missing, likely due to rotamers); HRMS-ESI (m/z) ([M]⁺) calcd forC₂₄H₃₇NO₇, 451.2558. found, 451.257.

Example 2 Step 1b: Preparation of tert-butylN-[(3S,7R,8R,9S)-8-benzyloxy-9-methyl-2-oxo-7-(p-tolylmethyl)oxonan-3-yl]-N-tert-butoxycarbonyl-carbamate(F230)

A 25 mL screw top vial was charged with tert-butyl((3S,7R,8R,9S)-8-(benzyloxy)-9-methyl-7-(4-methylbenzyl)-2-oxooxonan-3-yl)carbamate(720 mg, 1.50 mmol), DMAP (91.0 mg, 0.75 mmol), and anhydrous CH₃CN (7.5mL). To the mixture was added di-tert-butyl dicarbonate (1.30 g, 5.98mmol) and the reaction was stirred at room temperature for 17 h and thenwarmed to 50° C. and stirred for an additional 29 h. The reactionmixture was concentrated under a gentle stream of N₂ and the crudeconcentrate was purified by column chromatography on SiO₂ (gradient,0→20% acetone in hexane) to give tert-butyl((3S,7R,8R,9S)-8-(benzyloxy)-9-methyl-7-(4-methylbenzyl)-2-oxooxonan-3-yl)carbamateas a white solid (167 mg, 19%): mp 164-166° C.; ¹H NMR (400 MHz, CDCl₃)δ 7.41-7.26 (m, 5H), 7.07 (d, J=8.1 Hz, 2H), 7.03 (d, J=8.0 Hz, 2H),4.88-4.75 (m, 3H), 4.61 (d, J=10.8 Hz, 1H), 3.35 (t, J=9.1 Hz, 1H), 3.10(dd, J=13.3, 3.3 Hz, 1H), 2.40-2.28 (m, 4H), 2.22 (tt, J=13.5, 7.2 Hz,1H), 2.02-1.88 (m, 2H), 1.64-1.41 (m, 24H), 0.96-0.84 (m, 1H); ¹³C NMR(101 MHz, CDCl₃) δ 171.13, 152.83 (2C), 137.98, 137.51, 135.31, 129.01,128.77, 128.54, 127.89, 127.76, 84.14, 82.64 (2C), 75.44, 75.21, 57.57,45.77, 36.43, 30.83, 27.97 (6C), 26.84, 21.04, 19.67, 18.49; ESIMS m/z604 ([M+Na]⁺).

Example 3 Step 1: Preparation of tert-butyl((3S,7R,8R,9S)-8-(allyloxy)-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate

A solution of tert-butyl((3S,7R,8R,9S)-8-hydroxy-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate(350 mg, 0.775 mmol), palladium tetrakis(triphenylphosphine) (90 mg,0.078 mmol), and allyl tert-butyl carbonate (758 mg, 4.79 mmol) indegassed THF (3876 μl) was heated to 60° C. and stirred for 4 h. Thereaction mixture was cooled to room temperature and purified directly bycolumn chromatography on SiO₂ (EtOAc/Hex gradient) to afford the titleproduct as a light yellow oil (200 mg, 52.5%): IR (neat) 2977, 2934,2836, 1746, 1702, 1511, 1367, 1297, 1246, 1175 cm⁻¹; ¹H NMR (400 MHz,CDCl₃) δ 7.07 (d, J=8.5 Hz, 2H), 6.81 (d, J=8.6 Hz, 2H), 6.02-5.88 (m,1H), 5.33 (dd, J=17.2, 1.6 Hz, 1H), 5.20 (dd, J=10.4, 1.5 Hz, 1H),4.94-4.81 (m, 2H), 4.76 (t, J=10.3 Hz, 1H), 4.60-4.50 (m, 1H), 4.28 (dd,J=11.8, 5.6 Hz, 1H), 4.22-4.15 (m, 1H), 4.09 (dd, J=11.9, 5.3 Hz, 1H),3.78 (s, 3H), 3.30 (d, J=14.5 Hz, 3H), 3.21 (t, J=9.0 Hz, 1H), 3.03 (dd,J=13.5, 3.4 Hz, 1H), 2.34-2.22 (m, 1H), 2.15-1.98 (m, 1H), 1.80 (s, 1H),1.65-1.59 (m, 2H), 1.50-1.39 (m, 13H), 0.90-0.76 (m, 1H); ¹³C NMR (101MHz, CDCl₃) δ 173.53, 157.82, 134.40, 134.36, 132.63, 129.69, 117.12,113.73, 84.28, 84.24, 81.09, 74.62, 58.57, 57.06, 55.24, 55.22, 46.01,35.97, 28.32, 28.23, 26.57, 19.22, 18.26; HRMS-ESI (m/z) ([M]⁺) calcdfor C₂₇H₄₁NO₇, 491.2883. found, 491.2862.

Example 3 Step 2a: Preparation of tert-butyl((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-propoxyoxonan-3-yl)(methoxymethyl)carbamate(F221)

A vial was charged with 5 wt % Pd/C (26.0 mg, 0.012 mmol) and a solutionof tert-butyl((3S,7R,8R,9S)-8-(allyloxy)-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate(200 mg, 0.407 mmol) in EtOAc (1 mL). The vial was evacuated andbackfilled with H₂ (3×) and then stirred vigorously under one atmosphereof H₂ (balloon) at room temperature for 15 h. The reaction mixture wasfiltered through a plug of Celite® and concentrated to the titlecompound as a colorless oil (168 mg, 84%) IR (neat) 3368, 2973, 2936,2877, 1746, 1705, 1511, 1454, 1367, 1175 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ7.12-7.03 (m, 2H), 6.87-6.77 (m, 2H), 5.04-4.67 (m, 2H), 4.21-4.09 (m,1H), 3.78 (s, 3H), 3.71 (dtd, J=8.6, 6.8, 1.9 Hz, 1H), 3.50 (dtd, J=8.4,6.6, 1.7 Hz, 1H), 3.34-3.25 (m, 3H), 3.12 (td, J=9.3, 3.6 Hz, 1H),3.07-2.98 (m, 1H), 2.27 (ddd, J=13.4, 11.7, 6.2 Hz, 1H), 2.07 (s, 2H),1.76 (s, 1H), 1.71-1.54 (m, 4H), 1.55-1.33 (m, 14H), 0.97 (td, J=7.4,1.0 Hz, 3H), 0.81 (s, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 173.30, 157.80,132.75, 129.69, 113.73, 99.98, 84.02, 83.99, 81.11, 75.59, 75.52, 55.25,55.23, 46.20, 35.86, 35.82, 28.32, 26.56, 23.59, 19.21, 18.19, 18.12,10.75; HRMS-ESI (m/z) ([M]⁺) calcd for C₂₇H₄₃NO₇, 493.3040. found,493.3018.

Example 3 Step 2b-1: Preparation of tert-butyl((3S,7R,8R,9S)-7-(4-fluorobenzyl)-9-methyl-2-oxo-8-(2-oxoethoxy)oxonan-3-yl)(methoxymethyl)carbamate

A mixture of tert-butyl((3S,7R,8R,9S)-8-(allyloxy)-7-(4-fluorobenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate(480 mg, 1.001 mmol), NaHCO₃ (8.41 mg, 0.10 mmol) and anhydrous MeOH(0.31 mL) in anhydrous CH₂Cl₂ (9.7 mL) was treated with ozone at −78° C.until the solution became light blue in color. The mixture was purgedwith nitrogen until colorless and then quenched by addition of dimethylsulfide (0.148 mL, 2.00 mmol). The reaction mixture was warmed to roomtemperature and stirred for 20 h, concentrated, and purified by columnchromatography on SiO₂ (gradient, hexanes/EtOAc) to provide the titlecompound as a mixture of rotamers in the form of a white solid (461 mg,96%): mp 51-53° C.; IR (neat) 2935, 1740, 1701, 1509, 1367, 1297, 1173,1081 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 9.68 (s, 1H), 7.17-7.06 (m, 2H),7.00-6.91 (m, 2H), 4.99-4.16 (m, 6H), 3.87-2.97 (m, 4H), 2.46-2.27 (m,1H), 2.17-2.01 (m, 1H), 1.97-1.75 (m, 1H), 1.74-1.37 (m, 17H), 0.95-0.78(m, 1H); HRMS-ESI (m/z) ([M]⁺) calcd for C₂₅H₃₆FNO₇, 481.2476. found,481.2481.

Example 3 Step 2b-2: Preparation of tert-butyl((3S,7R,8R,9S)-8-(2,2-difluoro-ethoxy)-7-(4-fluorobenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate(F212)

To a solution of tert-butyl((3S,7R,8R,9S)-7-(4-fluorobenzyl)-9-methyl-2-oxo-8-(2-oxoethoxy)oxonan-3-yl)(methoxymethyl)carbamate(461 mg, 0.957 mmol) in anhydrous CH₂Cl₂ (6.0 mL) at 0° C. was added a˜50% toluene solution of Deoxo-Fluor® (0.710 mL, 1.92 mmol) in anhydrousCH₂Cl₂ (4 mL) dropwise at 0° C. and the reaction mixture was stirred at0° C. for 1 h. The reaction mixture was concentrated and purified bycolumn chromatography on SiO₂ (gradient, hexanes/EtOAc) to provide thetitle compound as a mixture of rotamers in the form of a white solid(399 mg, 83%): IR (neat) 2978, 2938, 1747, 1700, 1509, 1368, 1297, 1080cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.16-7.04 (m, 2H), 7.02-6.89 (m, 2H),5.86 (tt, J=55.1, 4.0 Hz, 1H), 4.95-4.71 (m, 3H), 4.60-4.46 (m, 0.5H),4.25-4.13 (m, 0.5H), 4.04-3.89 (m, 1H), 3.84-3.69 (m, 1H), 3.37-3.18 (m,3H), 3.03 (dd, J=13.3, 3.5 Hz, 1H), 2.41-2.30 (m, 1H), 2.19-1.99 (m,1H), 1.88-1.75 (m, 1H), 1.72-1.32 (m, 17H), 0.93-0.75 (m, 1H); ¹⁹F NMR(376 MHz, CDCl₃) δ−117.16, −117.27, −125.28-125.61 (m, 2F); HRMS-ESI(m/z) ([M]⁺) calcd for C₂₅H₃₆F₃NO₆, 503.2495. found, 503.2499.

Example 4 Step 1: tert-butyl((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-((3-oxobut-1-en-1-yl)oxy)oxonan-3-yl)(methoxymethyl)carbamate

A round bottomed flask was charged with tert-butyl((3S,7R,8R,9S)-8-hydroxy-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate(400 mg, 0.886 mmol) in CH₂Cl₂ (4429 μl). To the solution was addedDABCO (4.97 mg, 0.044 mmol) and the reaction mixture was cooled to 0° C.under N₂. Upon addition of but-3-yn-2-one (83 μl, 1.063 mmol), thecolorless solution became dark brown-orange. After stirring for 2 h, thereaction mixture was concentrated and purified directly by columnchromatography on SiO₂ (0→10%, hold, 10→20%, hold, 20→50% holdEtOAc/hexanes gradient) to afford the title compound as a thickcolorless oil (257 mg, 55.8%): ¹H NMR (400 MHz, CDCl₃) δ 7.43 (d, J=12.2Hz, 1H), 7.03 (d, J=8.6 Hz, 2H), 6.81 (d, J=8.6 Hz, 2H), 5.75 (d, J=12.4Hz, 1H), 5.06-4.85 (m, 2H), 4.82-4.73 (m, 1H), 4.61-4.50 (m, 1H),4.26-4.14 (m, 1H), 3.78 (s, 3H), 3.37-3.26 (m, 3H), 2.82 (dd, J=13.6,4.0 Hz, 1H), 2.41-2.28 (m, 1H), 2.24-2.01 (m, 1H), 2.18 (s, 3H),1.62-1.39 (m, 12H), 1.34 (d, J=6.4 Hz, 3H), 1.26 (t, J=7.1 Hz, 2H), 0.92(dt, J=13.6, 4.6 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 197.24, 173.18,163.24, 158.03, 155.34, 131.19, 129.61, 113.83, 108.08, 88.73, 88.61,81.19, 76.86, 76.23, 75.39, 72.61, 72.49, 58.42, 56.97, 55.41, 55.14,44.87, 35.82, 30.38, 29.45, 28.43, 28.27, 28.16, 26.38, 26.18, 19.16,18.24; ESIMS m/z 542.4 ([M+Na)]⁺).

Example 4 Step 2: Preparation of((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-(3-oxobutoxy)oxonan-3-yl)(methoxymethyl)carbamate

A round bottomed flask was charged with tert-butyl((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-((3-oxobut-1-en-1-yl)oxy)oxonan-3-yl)(methoxymethyl)-carbamate(257 mg, 0.495 mmol), 5 wt % Pd/C (35 mg, 0.033 mmol) and EtOAc (4 mL).The reaction flask was briefly evacuated under vacuum and backfilledwith H₂ (3×) and then stirred vigorously under an H₂ atmosphere at roomtemperature overnight. The reaction mixture was filtered through a plugof Celite® and concentrated to afford the title compound as a colorlessoil (256 mg, 99%): ¹H NMR (400 MHz, CDCl₃) δ 7.14-7.01 (m, 2H),6.87-6.77 (m, 2H), 4.94-4.73 (m, 3H), 4.08-3.95 (m, 1H), 3.88-3.71 (m,1H), 3.78 (s, 3H), 3.39-3.25 (m, 3H), 3.21-3.09 (m, 1H), 3.07-2.88 (m,1H), 2.70 (t, J=6.2 Hz, 1H), 2.37-2.22 (m, 1H), 2.20 (s, 2H), 1.80-1.59(m, 3H), 1.58-1.35 (m, 16H), 1.32-1.17 (m, 2H), 0.86-0.71 (m, 1H); ¹³CNMR (101 MHz, CDCl₃) δ 206.65, 173.53, 157.82, 132.63, 129.72, 129.68,113.81, 113.74, 84.56, 68.21, 55.23, 45.95, 43.90, 35.95, 30.73, 28.31,28.21, 21.05, 19.42, 19.26, 18.17; ESIMS m/z 544.3 ([M+Na]⁺).

Example 4 Step 3: Preparation of tert-butyl((3S,7R,8R,9S)-8-(3,3-difluorobutoxy)-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate(F218)

A 20 mL vial was charged with tert-butyl((3S,7R,8R,9S)-7-(4-methoxybenzyl)-9-methyl-2-oxo-8-(3-oxobutoxy)oxonan-3-yl)(methoxymethyl)carbamate(250 mg, 0.479 mmol), CH₂Cl₂ (3 mL) and Deoxo-Fluor® (1.04 g, 2.35 mmol)and the mixture was stirred vigorously at room temperature under N₂ for12 h. An additional portion of Deoxo-Fluor® (900 mg, 4.07 mmol) wasadded and reaction was stirred for an additional 48 h. Upon completeconsumption of starting material, the reaction mixture was quenched(carefully!) with saturated aqueous NaHCO₃ solution and extracted withCH₂Cl₂ (3×). The mixture was passed through a phase separator and theorganic phase was concentrated, and purified by column chromatography onSiO₂ (gradient, hexanes/EtOAc) to provide the title compound as acolorless oil (106.6 mg, 40.9%): ¹H NMR (400 MHz, CDCl₃) d 7.10-7.00 (m,2H), 6.88-6.76 (m, 2H), 4.97-4.82 (m, 2H), 4.81-4.71 (m, 1H), 4.55 (s,1H), 4.19 (t, J=9.6 Hz, 1H), 3.97-3.84 (m, 1H), 3.78 (s, 3H), 3.72 (dt,J=9.1, 6.8 Hz, 1H), 3.37-3.26 (m, 3H), 3.14 (td, J=8.9, 3.2 Hz, 1H),2.97 (dd, J=13.4, 3.5 Hz, 1H), 2.37-2.24 (m, 1H), 2.26-2.02 (m, 3H),1.81-1.57 (m, 5H), 1.58-1.23 (m, 14H), 0.89-0.77 (m, 1H); ¹⁹F NMR (376MHz, CDCl₃) d −89.52, −89.56 (d, J=72.5 Hz); ESIMS m/z 566.3 ([M+Na]⁺).

Example 5 Preparation of(2S,3R,4R,8S)-8-((tert-butoxycarbonyl)-(methoxymethyl)-amino)-4-(4-methoxybenzyl)-2-methyl-9-oxooxonan-3-ylcyclopentanecarboxylate (F217)

A 20 mL vial was charged with tert-butyl((3S,7R,8R,9S)-8-hydroxy-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate(200 mg, 0.443 mmol), CH₂Cl₂ (2215 μl), NEt₃ (185 μl, 1.329 mmol) andDMAP (5.41 mg, 0.044 mmol). The reaction mixture was cooled to 0° C. inan ice bath under N₂ and cyclopentanecarbonyl chloride (76 mg, 0.576mmol) was added in one portion. The reaction became darkbrownish-yellow. After stirring for 2 h, the reaction mixture wasquenched by the addition of saturated aqueous NaHCO₃. The mixture wasextracted with CH₂Cl₂ (3×) and the combined organic layers were washedwith brine, dried over MgSO4, concentrated, and purified by columnchromatography on SiO₂ (0→100% EtAOx/hexanes) to provide the titlecompound as a yellow solid (85 mg, 35.0%): ¹H NMR (400 MHz, CDCl₃) δ7.01 (d, J=8.5 Hz, 4H), 6.81 (d, J=8.4 Hz, 4H), 5.06-4.85 (m, 3H), 4.77(d, J=11.6 Hz, 1H), 4.57 (dd, J=10.7, 6.0 Hz, 0H), 4.29-4.17 (m, 1H),3.78 (s, 3H), 3.38-3.26 (m, 3H), 2.74 (p, J=8.0 Hz, 1H), 2.61 (dd,J=13.7, 3.7 Hz, 1H), 2.31 (dd, J=13.7, 11.1 Hz, 1H), 2.20-2.07 (m, 1H),1.99-1.52 (m, 8H), 1.51-1.40 (m, 9H), 1.27 (d, J=5.8 Hz, 3H), 1.15-0.96(m, 1H), 0.97-0.87 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ 176.26, 173.56,157.94, 155.49, 131.94, 129.59, 113.80, 81.21, 75.54, 72.72, 58.52,55.43, 55.22, 44.32, 44.04, 35.77, 30.09, 30.00, 29.58, 28.20, 26.48,25.72, 25.70, 19.09, 17.56; ESIMS m/z 570.5 ([M+Na]⁺).

Example 6 Preparation of tert-butyl((3S,7R,8R,9S)-7-isopentyl-8-methoxy-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate(F205)

To an oven-dried vial were addedN1,N1,N8,N8-tetramethylnaphthalene-1,8-diamine (Proton Sponge®; 1.63 g,7.60 mmol), tert-butyl((3S,7R,8R,9S)-8-hydroxy-7-isopentyl-9-methyl-2-oxooxonan-3-yl)(methoxymethyl)carbamate(436 mg, 1.086 mmol), anhydrous Na₂SO₄ (1.15 g, 8.10 mmol), andtrimethyloxonium tetrafluoroborate (723 mg, 4.89 mmol) in anhydrousCH₂Cl₂ (11 mL) at 0° C. The reaction mixture was slowly warmed to roomtemperature and stirred for 5 h. The reaction mixture was diluted withEtOAc, filtered, and the filtrate was washed with water. The phases wereseparated and the aqueous phase was extracted with additional EtOAc, andthe combined organic phases were washed with 1.0 M aqueous sodiumbisulfate (NaHSO₄), washed with saturated aqueous NaHCO₃, dried overMgSO₄, concentrated, and purified by column chromatography on SiO₂(gradient, hexanes/EtOAc) to provide the title compound as a mixture ofrotamers in the form of a white solid (320 mg, 71%): IR (neat) 2934,1747, 1705, 1454, 1366, 1296, 1170, 1080 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ4.97-4.70 (m, 3H), 4.60-4.47 (m, 0.5H), 4.25-4.11 (m, 0.5H), 3.49 (s,3H), 3.40-3.28 (m, 3H), 2.97-2.86 (m, 1H), 2.17-2.01 (m, 1H), 1.79-1.42(m, 16H), 1.42 (d, J=6.4 Hz, 3H), 1.31-1.07 (m, 3H), 0.99-0.82 (m, 7H);¹³C NMR (101 MHz, CDCl₃) δ 173.54, 155.56, 155.39, 86.39, 81.02, 80.98,76.34, 75.50, 74.70, 74.43, 61.04, 58.62, 57.11, 55.45, 55.36, 43.42,36.40, 30.67, 29.62, 28.20, 28.15, 28.09, 27.31, 27.04, 23.05, 22.12,19.19, 18.10; HRMS-ESI (m/z) ([M]⁺) calcd for C₂₂H₄₁NO₆, 415.2934.found, 415.2943.

Example 7 Step 1: Preparation of tert-butyl((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate

To a solution of tert-butyl((3S,7R,8R,9S)-7-(2-((tert-butyldimethylsilyl)-oxy)ethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate(3.01 g, 5.77 mmol) in anhydrous THF (58 mL) was added a 1M solution ofTBAF in THF (8.65 ml, 8.65 mmol). The resulting yellow solution wasstirred at room temperature for 4 h, poured into 100 mL 1/2 saturatedNaCl solution, and extracted with EtOAc (3×50 mL). The organic extractswere combined, dried over MgSO₄, filtered, and concentrated to provide alight yellow oil, which was purified by column chromatography on SiO₂(5→25% acetone/hexanes) to provide the title compound as a hard whitefoam (1.95 g, 83%): ¹H NMR (400 MHz, CDCl₃) δ 7.44-7.17 (m, 2H), 6.95(t, J=8.2 Hz, 3H), 5.17-4.98 (m, 2H), 4.29-4.11 (m, 2H), 3.75-3.53 (m,2H), 2.28 (dt, J=13.4, 6.7 Hz, 1H), 2.03-1.88 (m, 1H), 1.88-1.74 (m,2H), 1.74-1.62 (m, 1H), 1.62-1.48 (m, 2H), 1.44 (s, 10H), 1.28 (d, J=6.5Hz, 3H), 1.26-1.19 (m, 1H), 1.14 (ddd, J=15.1, 7.5, 3.6 Hz, 1H); ¹³C NMR(101 MHz, CDCl₃) δ 173.30, 159.23, 154.90, 129.69, 121.20, 115.33,80.99, 79.92, 74.68, 60.96, 52.99, 39.55, 34.07, 28.56, 28.33, 19.13,18.36; ESIMS m/z 408.3 ([M+H]⁺), 430.3 ([M+Na]⁺).

Example 7 Step 2a: Preparation of tert-butyl((3S,7R,8R,9S)-9-methyl-2-oxo-8-phenoxy-7-(2-phenoxyethyl)oxonan-3-yl)carbamate(F240)

To a solution of tert-butyl((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate(215 mg, 0.528 mmol) in anhydrous toluene (5.3 mL) were addedPh₃Bi(OAc)₂ (354 mg, 0.633 mmol), diacetoxycopper (19.17 mg, 0.106mmol), and N-cyclohexyl-N-methylcyclohexanamine (224 μl, 1.055 mmol).The resulting mixture was heated to 50° C. for 20 h, cooled to roomtemperature, filtered through a plug of Celite®, and rinsed the plugwith toluene. The filtrate was concentrated and purified by columnchromatography on SiO₂ (2→20% acetone/hexanes) to provide the titlecompound as a sticky oil (253 mg). ¹H NMR gives the desired product, butit is contaminated with Cy₂NMe. The oil was dissolved in CH₂Cl₂ (25 mL)and the solution was washed with 0.2 M HCl (25 mL), dried over Na₂SO₄,decanted, and concentrated to provide 234 mg of the desired product as ahard white foam. The product was repurified by column chromatography onSiO₂ (5→20% acetone/hexanes) to provide the title compound as a hardwhite foam (199 mg, 78%): ¹H NMR (400 MHz, CDCl₃) δ 7.33-7.20 (m, 4H),6.93 (p, J=7.4 Hz, 4H), 6.86-6.75 (m, 2H), 5.21-4.97 (m, 2H), 4.32-4.11(m, 2H), 3.94 (t, J=6.6 Hz, 2H), 2.34-2.22 (m, 1H), 2.06 (dd, J=16.4,4.9 Hz, 2H), 1.93 (d, J=12.6 Hz, 1H), 1.89-1.78 (m, 1H), 1.78-1.65 (m,2H), 1.44 (s, 9H), 1.31 (d, J=6.5 Hz, 3H), 1.19 (dd, J=25.8, 13.7 Hz,2H); ¹³C NMR (101 MHz, CDCl₃) δ 173.28, 159.34, 158.76, 154.89, 129.68,129.39, 121.17, 120.61, 115.40, 114.42, 99.98, 81.14, 79.92, 74.68,66.01, 53.01, 40.14, 34.11, 30.49, 19.20, 18.35; ESIMS m/z 484.3([M+H]⁺).

Example 7 Step 2b: Preparation of tert-butyl((3S,7R,8R,9S)-7-(2-methoxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate(F242)

To a solution of tert-butyl((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate(400 mg, 0.982 mmol) and Proton Sponge® (841 mg, 3.93 mmol) in anhydrousCH₂Cl₂ (10 mL) at 0° C. (icewater bath) was added trimethyloxoniumtetrafluoroborate (290 mg, 1.963 mmol; weighed under N₂), and theresulting mixture was stirred at 0° C. for 3 h, quenched with 1N HCl (20mL), and extracted with CH₂Cl₂ (3×20 mL). The organic extracts werecombined, dried over Na₂SO₄, filtered, and concentrated to provide anoily white solid, which was purified by column chromatography on SiO₂(5→20% acetone/hexanes) to provide the title compound as a white,crystalline solid (321 mg, 78%): ¹H NMR (400 MHz, CDCl₃) δ 7.27 (t,J=8.0 Hz, 2H), 6.94 (dd, J=7.7, 3.3 Hz, 3H), 5.10 (d, J=8.1 Hz, 1H),5.08-4.98 (m, 1H), 4.20 (q, J=7.9, 6.9 Hz, 2H), 3.36 (t, J=6.5 Hz, 2H),3.25 (s, 3H), 2.27 (dt, J=13.3, 6.8 Hz, 1H), 1.88 (ddt, J=10.8, 6.9, 3.9Hz, 2H), 1.83-1.71 (m, 1H), 1.70-1.61 (m, 1H), 1.60-1.52 (m, 1H), 1.44(s, 10H), 1.28 (d, J=6.5 Hz, 3H), 1.25-1.16 (m, 1H), 1.16-1.05 (m, 1H);¹³C NMR (101 MHz, CDCl₃) δ 173.28, 159.46, 154.90, 129.61, 121.05,115.38, 81.12, 79.86, 74.71, 70.79, 58.42, 52.99, 40.09, 34.12, 30.53,28.33, 28.15, 19.07, 18.36; ESIMS m/z 422.3 ([M+H]⁺), 444.3 ([M+Na]⁺).

Example 7 Step 2c-1: Preparation of tert-butyl((3S,7R,8R,9S)-9-methyl-2-oxo-7-(2-oxoethyl)-8-phenoxyoxonan-3-yl)carbamate

To a solution of tert-butyl((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate(250 mg, 0.613 mmol) in CH₂Cl₂ (6.1 mL) at 0° C. was added Dess-Martinperiodinane (286 mg, 0.675 mmol). The resulting mixture was stirred at0° C. for 2 h, quenched with sat. aqueous sodium thiosulfate (Na₂S₂O₃; 3mL) and sat. aqueous NaHCO₃ (3 mL) solution, and then removed from thecold bath and stirred vigorously for 10 min. The phases were separatedand the aqueous phase was extracted with CH₂Cl₂ (2×6 mL) and thecombined organic extracts were dried over Na₂SO₄, filtered, andconcentrated to provide the title compound as a fluffy white foam (255.4mg, 98%): ¹H NMR (400 MHz, CDCl₃) δ 9.65 (t, J=1.7 Hz, 1H), 7.29 (dd,J=8.7, 7.4 Hz, 2H), 7.02-6.93 (m, 1H), 6.88 (d, J=7.9 Hz, 2H), 5.23-5.08(m, 2H), 4.30-4.10 (m, 2H), 2.60 (dd, J=16.0, 5.4 Hz, 1H), 2.44 (d,J=6.4 Hz, 1H), 2.38-2.21 (m, 2H), 1.73 (ddd, J=19.5, 13.8, 9.2 Hz, 3H),1.44 (s, 9H), 1.37-1.22 (m, 5H); ¹³C NMR (101 MHz, CDCl₃) δ 200.78,173.29, 158.65, 154.90, 129.80, 129.73, 121.59, 115.23, 80.63, 79.98,74.23, 53.28, 46.09, 36.71, 33.64, 31.78, 28.33, 19.72, 18.18; ESIMS m/z428.2 ([M+Na]⁺).

Example 7 Step 2c-2: Preparation of tert-butyl((3S,7R,8R,9S)-7-(2,2-difluoroethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate

To a solution of tert-butyl((3S,7R,8R,9S)-9-methyl-2-oxo-7-(2-oxoethyl)-8-phenoxyoxonan-3-yl)carbamate(241 mg, 0.594 mmol) in anhydrous CH₂Cl₂ (6 mL) at 0° C. (icewater bath)was added Deoxo-Fluor® (230 μl, 1.248 mmol). The reaction was stirredfor 2.5 h, concentrated, and purified by column chromatography on SiO₂(2→20% acetone/hexanes) to provide the title compound as a whitecrystalline solid (153.2 mg, 60.3%): ¹H NMR (400 MHz, CDCl₃) δ 7.29(dtd, J=10.1, 4.8, 2.5 Hz, 2H), 7.01-6.95 (m, 1H), 6.93 (d, J=8.0 Hz,2H), 5.83 (tt, J=57.0, 4.6 Hz, 1H), 5.18-5.00 (m, 2H), 4.21 (q, J=8.7Hz, 2H), 2.29 (dt, J=13.4, 6.8 Hz, 1H), 2.12-1.94 (m, 2H), 1.91-1.77 (m,2H), 1.77-1.70 (m, 1H), 1.66-1.54 (m, 1H), 1.44 (s, 9H), 1.30 (d, J=6.5Hz, 3H), 1.27-1.16 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 173.21, 158.93,154.89, 129.83, 121.55, 116.74 (t, J=239.4 Hz), 115.25, 80.57, 79.97,74.39, 53.02, 37.53, 35.74 (t, J=21.1 Hz), 33.86, 29.44, 28.32, 19.21,18.27; ESIMS m/z 450.3 ([M+Na)⁺]).

Example 7 Step 2d-1: Preparation of tert-butyl((3S,7R,8R,9S)-7-(2-bromoethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate(F249)

To a solution of tert-butyl((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate(700 mg, 1.718 mmol) in CH₂Cl₂ (17 mL) at 0° C. (icewater bath) wereadded perbromomethane (627 mg, 1.890 mmol) and triphenylphosphine (541mg, 2.061 mmol). After 70 min, TLC (2:1 hexanes:acetone) showedincomplete conversion so additional CBr₄ and Ph₃P (64 mg and 54 mg,respectively) were added and the reaction was stirred for an additional20 min. The reaction was concentrated and purified by columnchromatography on SiO₂ (5→20% acetone/hexanes) to provide the titlecompound as a hard white foam (712 mg, 88%): ¹H NMR (400 MHz, CDCl₃) δ7.39-7.27 (m, 2H), 7.03-6.82 (m, 3H), 5.18-4.99 (m, 2H), 4.21 (q, J=8.7Hz, 2H), 3.44 (ddd, J=10.0, 7.4, 5.0 Hz, 1H), 3.33 (ddd, J=9.9, 8.4, 6.9Hz, 1H), 2.28 (dt, J=13.0, 6.6 Hz, 1H), 2.10 (dtd, J=12.6, 7.9, 4.5 Hz,1H), 2.05-1.96 (m, 1H), 1.85-1.73 (m, 2H), 1.73-1.61 (m, 1H), 1.44 (s,10H), 1.30 (d, J=6.5 Hz, 3H), 1.28-1.20 (m, 1H), 1.20-1.09 (m, 1H); ¹³CNMR (101 MHz, CDCl₃) δ 173.20, 159.18, 154.89, 129.74, 121.33, 115.37,80.94, 79.95, 74.57, 53.02, 41.18, 34.13, 33.95, 31.54, 28.33, 19.13,18.29; HRMS-ESI (m/z) ([M+Na]⁺) calcd for C₂₂H₃₂BrNNaO₅, 492.1356.found, 492.1352.

Example 7 Step 2d-2: Preparation of tert-butyl((3S,7S,8R,9S)-7-ethyl-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate(F250)

To a solution of tert-butyl((3S,7R,8R,9S)-7-(2-bromoethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate(408 mg, 0.867 mmol) and AIBN (14.24 mg, 0.087 mmol) in anhydroustoluene (8.7 mL) was added Bu₃SnH (257 μl, 0.954 mmol), and the reactionwas heated to 80° C. After 1 h, TLC (4:1 hexanes:acetone) still showedstarting material. An additional 0.5 equivalents of Bu₃SnH and 0.05equiv AIBN were added and the reaction was stirred for an additional 1 hat 80° C. The reaction was cooled to room temperature, stirred with 10%aqueous potassium fluoride (KF) solution (7 mL) for 20 h, andpartitioned between Et₂O (20 mL) and sat. NaCl solution (20 mL). Thephases were separated and the aqueous phase was extracted with Et₂O(2×20 mL). The organic extracts were combined, dried over MgSO₄,filtered and concentrated to provide a white solid, which was purifiedby column chromatography on SiO₂ (5→20% acetone/hexanes) to provide thetitle compound as a white solid (295 mg, 87%): ¹H NMR (400 MHz, CDCl₃) δ7.38-7.16 (m, 2H), 7.00-6.87 (m, 3H), 5.19-4.97 (m, 2H), 4.18 (t, J=8.8Hz, 2H), 2.27 (dt, J=13.1, 6.7 Hz, 1H), 1.91-1.77 (m, 1H), 1.70-1.58 (m,3H), 1.58-1.48 (m, 1H), 1.44 (s, 9H), 1.28 (d, J=6.5 Hz, 3H), 1.25-1.14(m, 2H), 1.12-1.01 (m, 1H), 0.86 (t, J=7.3 Hz, 3H); ¹³C NMR (101 MHz,CDCl₃) δ 173.34, 159.68, 154.91, 129.58, 120.95, 115.40, 81.44, 79.86,74.74, 53.00, 44.96, 34.20, 28.34, 27.85, 27.03, 26.85, 23.50, 18.74,18.40, 17.53, 13.61, 11.86; ESIMS m/z 392.3 ([M+H]⁺), 414.3 ([M+Na]⁺).

Example 7 Step 2e: Preparation of((3S,7R,8R,9S)-7-(2-fluoroethyl)-8-isobutoxy-9-methyl-2-oxooxonan-3-yl)carbamate(F235)

To a solution of tert-butyl((3S,7R,8R,9S)-7-(2-hydroxyethyl)-8-isobutoxy-9-methyl-2-oxooxonan-3-yl)carbamate(200 mg, 0.516 mmol) in anhydrous chloroform (CHCl₃; 5.1 mL) at 0° C.(icewater bath) was added Deoxo-Fluor® (114 μl, 0.619 mmol). Theresulting solution was stirred at 0° C. for 4 h, poured into H₂O (20 mL)and extracted with CH₂Cl₂ (3×20 mL). The organic extracts were combined,dried over Na₂SO₄, filtered, and concentrated to provide a yellow solid,which was purified by column chromatography on SiO₂ (2→25%acetone/hexanes) to provide the title compound as a white solid (177 mg,88%) as a white solid: ¹H NMR (400 MHz, CDCl₃) δ 5.07 (d, J=8.1 Hz, 1H),4.92-4.78 (m, 1H), 4.55 (td, J=5.6, 3.2 Hz, 1H), 4.47-4.37 (m, 1H), 4.15(dt, J=10.7, 7.8 Hz, 1H), 3.43 (dd, J=8.4, 6.6 Hz, 1H), 3.24 (dd, J=8.4,6.4 Hz, 1H), 3.09-2.96 (m, 1H), 2.22 (dt, J=13.4, 6.7 Hz, 1H), 2.10-1.95(m, 1H), 1.83 (dp, J=13.2, 6.6 Hz, 1H), 1.67 (d, J=7.9 Hz, 3H),1.64-1.53 (m, 2H), 1.44 (s, 9H), 1.40 (d, J=6.4 Hz, 3H), 1.17 (q, J=11.6Hz, 1H), 1.08-0.97 (m, 1H), 0.94-0.88 (m, 6H); ¹³C NMR (101 MHz, CDCl₃)δ 173.30, 154.91, 83.83, 83.78, 82.14, 80.21, 79.82, 75.14, 52.97,39.75, 34.06, 31.57, 31.37, 29.15, 28.69, 28.32, 19.44, 19.40, 19.07,18.14; ESIMS m/z 412.3 ([M+Na]⁺).

Example 7 Step 2f-1: Preparation of tert-butyl((3S,7R,8R,9S)-9-methyl-7-(2-((2-nitrophenyl)selanyl)ethyl)-2-oxo-8-phenoxyoxonan-3-yl)carbamate

To a solution of tert-butyl((3S,7R,8R,9S)-7-(2-hydroxyethyl)-9-methyl-2-oxo-8-phenoxyoxonan-3-yl)carbamate(227 mg, 0.557 mmol) in anhydrous THF (5.6 mL) at 0° C. (ice water bath)were added 1-nitro-2-selenocyanatobenzene (177 mg, 0.780 mmol) andtributylphosphine (223 μl, 0.891 mmol). The resulting solution wasstirred for 3 h and then treated with additional1-nitro-2-selenocyanatobenzene and tributylphospine (53 mg and 67 μL,respectively). The reaction was stirred for an additional 1 h, thenpoured into 20 mL sat. NaCl solution and extracted with 3×20 mL EtOAc.The organic extracts were combined, dried over MgSO₄, filtered, andconcentrated to provide a brown oil, which was purified by columnchromatography on SiO₂ (2→20% acetone/hexanes) to provide the titlecompound as a bright yellow solid (294 mg, 89%): ¹H NMR (400 MHz, CDCl₃)δ 8.24 (dt, J=8.2, 1.0 Hz, 1H), 7.36-7.19 (m, 5H), 7.00-6.92 (m, 1H),6.92-6.84 (m, 2H), 5.16-4.98 (m, 2H), 4.21 (t, J=8.5 Hz, 2H), 3.05-2.76(m, 2H), 2.30 (dt, J=13.2, 6.7 Hz, 1H), 1.94 (tdq, J=28.6, 14.1, 8.4,6.4 Hz, 3H), 1.78-1.64 (m, 2H), 1.60 (d, J=4.5 Hz, 1H), 1.45 (s, 9H),1.30 (d, J=6.5 Hz, 3H), 1.27-1.13 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ173.23, 159.12, 154.89, 146.86, 133.45, 133.21, 129.76, 128.95, 126.41,125.29, 121.34, 115.33, 80.99, 79.97, 74.59, 52.99, 43.60, 34.00, 29.99,28.58, 28.33, 24.24, 19.15, 18.29; ESIMS m/z 593.2 ([M+Na]⁺).

Example 7 Step 2f-2: Preparation of tert-butyl((3S,7R,8R,9S)-9-methyl-2-oxo-8-phenoxy-7-vinyloxonan-3-yl)carbamate(F259)

To a solution of tert-butyl((3S,7R,8R,9S)-9-methyl-7-(2-((2-nitrophenyl)-selanyl)ethyl)-2-oxo-8-phenoxyoxonan-3-yl)carbamate(284 mg, 0.480 mmol) in THF (4.8 mL) was added 30% aqueous hydrogenperoxide (H₂O₂ 392 μl, 3.84 mmol), and the resulting bright yellowsolution was stirred at room temperature for 3 d. The reaction wascooled to 0° C. (icewater bath), quenched with sat. aqueous NaHSO₃solution (4 mL), diluted with H₂O (20 mL), and extracted with EtOAc(3×20 mL). The organic extracts were combined, dried over MgSO₄,filtered, and concentrated to the title compound as an orange solid(134.9 mg, 72%): ¹H NMR (400 MHz, CDCl₃) δ 7.34-7.19 (m, 2H), 7.02-6.86(m, 3H), 5.76 (ddd, J=17.2, 10.3, 8.0 Hz, 1H), 5.17-5.06 (m, 2H), 5.03(d, J=17.1 Hz, 1H), 4.94 (d, J=10.4 Hz, 1H), 4.28 (t, J=8.8 Hz, 1H),4.25-4.17 (m, 1H), 2.56-2.41 (m, 1H), 2.27 (dt, J=13.5, 6.6 Hz, 1H),1.85 (td, J=14.6, 7.1 Hz, 1H), 1.75 (dt, J=14.8, 7.3 Hz, 1H), 1.65 (s,1H), 1.44 (s, 9H), 1.33 (d, J=6.4 Hz, 3H), 1.31-1.17 (m, 2H); ¹³C NMR(101 MHz, CDCl₃) δ 173.35, 159.33, 138.51, 129.49, 121.10, 116.18,115.78, 99.98, 80.46, 74.39, 53.05, 47.47, 34.13, 31.07, 28.34, 19.66,18.36; HRMS-ESI (m/z) ([M+Na]⁺) calcd for C₂₂H₃₁NO₅Na, 412.2094. found412.2106.

Example 8 Step 1: Preparation of(3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-aminiumchloride (F244)

A 25 mL screw top vial was charged with tert-butyl((3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-yl)carbamate(300 mg, 0.642 mmol), anhydrous CH₂Cl₂ (4 mL), and 4.0 M HCl in dioxane(3.21 mL, 12.83 mmol). After stirring at room temperature for 80 min,the reaction mixture was concentrated under a stream of nitrogen anddried under high vacuum to provide the title compound as a beige solid(259 mg, 100%): mp 200-210° C. (dec.); ¹H NMR (400 MHz, CDCl₃) δ7.46-6.81 (m, 9H), 5.14 (s, 1H), 3.78-3.52 (m, 3H), 2.86 (s, 1H),2.60-1.12 (m, 12H), 0.96 (s, 1H); ¹³C NMR (101 MHz, CD₃OD) δ 171.05,160.65, 137.89, 136.19, 130.75, 129.87, 129.75, 122.14, 117.03, 81.89,76.55, 68.05, 46.67, 37.46, 32.38, 27.71, 21.05, 20.12, 18.85; ESIMS m/z369 ([M+H]⁺).

Example 8 Step 2: Preparation of3-hydroxy-4-methoxy-N-((3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-yl)picolinamide(F49)

A 25 mL screw top vial was charged with(3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-aminiumchloride (259 mg, 0.642 mmol), 3-hydroxy-4-methoxypicolinic acid (122mg, 0.721 mmol), anhydrous CH₂Cl₂ (6.5 mL), andN,N-diisopropylethylamine (340 μL, 1.95 mmol). To the mixture was addedPyBOP (376 mg, 0.723 mmol) and the reaction was stirred at roomtemperature for 1.5 h and then directly purified by columnchromatography on SiO₂ (2→30% acetone/hexanes) to provide the titlecompound as a white solid (162 mg, 49%): mp 62-66° C.; ¹H NMR (400 MHz,CDCl₃) δ12.09 (s, 1H), 8.48 (d, J=8.2 Hz, 1H), 7.98 (d, J=5.1 Hz, 1H),7.37-7.28 (m, 2H), 7.12-6.93 (m, 7H), 6.86 (d, J=5.2 Hz, 1H), 5.14 (dq,J=9.2, 6.4 Hz, 1H), 4.62 (dt, J=10.9, 7.4 Hz, 1H), 4.35 (t, J=8.9 Hz,1H), 3.93 (s, 3H), 2.99 (dd, J=13.3, 3.2 Hz, 1H), 2.42-2.26 (m, 5H),2.16-2.04 (m, 1H), 1.79-1.52 (m, 3H), 1.41-1.23 (m, 4H), 1.08-0.98 (m,1H); ¹³C NMR (101 MHz, CDCl₃) δ 172.06, 168.59, 159.58, 155.27, 148.66,140.47, 136.92, 135.38, 130.28, 129.63, 128.98, 128.59, 121.16, 115.48,109.43, 81.02, 74.89, 55.99, 51.43, 45.59, 36.34, 33.47, 26.57, 20.95,18.78, 18.33; ESIMS: m/z 519 ([M+H]⁺).

Example 9 Preparation of((2-(((3S,7R,8R,9S)-7-(2-fluoroethyl)-8-isobutoxy-9-methyl-2-oxooxonan-3-yl)carbamoyl)-4-methoxypyridin-3-yl)oxy)methylacetate (F128)

To a solution ofN-((3S,7R,8R,9S)-7-(2-fluoroethyl)-8-isobutoxy-9-methyl-2-oxooxonan-3-yl)-3-hydroxy-4-methoxypicolinamide(97 mg, 0.220 mmol) in anhydrous acetone (2.2 mL) were added powderedK₂CO₃ (60.9 mg, 0.440 mmol) and bromomethyl acetate (32.4 μl, 0.330mmol). The resulting mixture was heated to 50° C. and stirred vigorouslyfor 16 h, then filtered through a plug of Celite®, concentrated, andpurified by column chromatography on SiO₂ (5→50% acetone/hexanes) toprovide the title compound as a sticky solid (87 mg, 77%): ¹H NMR (400MHz, CDCl₃) δ 8.34 (d, J=8.1 Hz, 1H), 8.28 (d, J=5.4 Hz, 1H), 6.95 (d,J=5.4 Hz, 1H), 5.74 (s, 2H), 4.90 (dq, J=9.1, 6.4 Hz, 1H), 4.58 (ddt,J=9.4, 5.9, 4.6 Hz, 2H), 4.50-4.39 (m, 1H), 3.91 (s, 3H), 3.45 (dd,J=8.4, 6.6 Hz, 1H), 3.26 (dd, J=8.4, 6.4 Hz, 1H), 3.14-3.02 (m, 1H),2.36 (dt, J=12.9, 6.7 Hz, 1H), 2.07 (s, 3H), 2.06-1.98 (m, 1H), 1.84(dp, J=13.4, 6.7 Hz, 1H), 1.78-1.60 (m, 4H), 1.57 (s, 1H), 1.42 (d,J=6.4 Hz, 3H), 1.39-1.29 (m, 1H), 1.10 (dd, J=14.3, 5.7 Hz, 1H), 0.92(d, J=6.8 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 170.35, 167.84, 160.52,157.81, 143.31, 141.51, 140.02, 107.14, 87.11, 81.42, 81.36, 79.73,77.78, 72.81, 53.74, 49.43, 37.34, 37.30, 31.13, 29.17, 28.98, 26.73,26.26, 18.44, 17.02, 16.98, 16.74, 15.69; HRMS-ESI (m/z) ([M+Na]⁺) calcdfor C₂₅H₃₇FN₂O₈Na, 535.2426. found 535.2423.

Example 10 Preparation of4-methoxy-2-(((3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-yl)carbamoyl)pyridin-3-ylacetate (F79)

A 25 mL screw top vial was charged with3-hydroxy-4-methoxy-N-((3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-phenoxyoxonan-3-yl)picolinamide(74.0 mg, 0.143 mmol), DMAP (19.4 mg, 0.159 mmol), 1,2-dichloroethane(DCE; 1 mL), acetyl chloride (20 μL, 0.281 mmol), and NEt₃ (70 μL, 0.502mmol). The resulting mixture was heated to 50° C. for 7 h. After coolingto room temperature, the crude reaction mixture was directly purified bycolumn chromatography on SiO₂ (2→40% acetone/hexanes) to provide thetitle compound as a white solid (56.0 mg, 70%): mp 96-100° C.; ¹H NMR(400 MHz, CDCl₃) δ 8.53 (d, J=8.4 Hz, 1H), 8.33 (d, J=5.5 Hz, 1H),7.36-7.27 (m, 2H), 7.12-6.92 (m, 8H), 5.12 (dq, J=9.1, 6.4 Hz, 1H), 4.63(dt, J=10.9, 7.5 Hz, 1H), 4.33 (t, J=8.9 Hz, 1H), 3.89 (s, 3H), 2.97(dd, J=13.3, 3.2 Hz, 1H), 2.41 (s, 3H), 2.32 (d, J=9.3 Hz, 5H),2.14-2.03 (m, 1H), 1.73-1.48 (m, 3H), 1.39-1.19 (m, 5H); ¹³C NMR (101MHz, CDCl₃) δ 172.55, 168.83, 162.34, 159.62, 159.36, 146.65, 141.31,137.42, 137.01, 135.34, 129.62, 128.96, 128.61, 121.12, 115.50, 109.76,81.10, 74.64, 56.22, 51.52, 45.62, 36.35, 33.75, 26.67, 20.95, 20.69,18.83, 18.31; ESIMS: m/z 561 ([M+H]⁺).

Example 11 Preparation of2-(((3S,7R,8R,9S)-8-(cyclopropylmethoxy)-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)carbamoyl)-4-methoxypyridin-3-yl3-methoxypropanoate (F195)

To a 4 mL vial were addedN-((3S,7R,8R,9S)-8-(cyclopropylmethoxy)-7-(4-methoxybenzyl)-9-methyl-2-oxooxonan-3-yl)-3-hydroxy-4-methoxypicolinamide(85 mg, 0.166 mmol), CH₂Cl₂ (1 mL) and NEt₃ (0.069 mL, 0.497 mmol),3-methoxypropanoyl chloride (30.5 mg, 0.249 mmol), and DMAP (3 mg, 0.02mmol), and the resulting light yellow solution was stirred at roomtemperature overnight. The reaction mixture was concentrated andpurified by column chromatography on SiO₂ (0→100% EtOAc/hexanes) toprovide the title compound as a colorless semi-solid (77.8 mg, 78%): IR(neat) 3381, 2936, 1769, 1742, 1678, 1511, 1246, 1111 cm⁻¹; ¹H NMR (400MHz, CDCl₃) δ 8.47 (d, J=7.3 Hz, 1H), 8.31 (d, J=5.4 Hz, 1H), 7.09 (d,J=8.6 Hz, 2H), 6.98 (d, J=5.5 Hz, 1H), 6.83 (d, J=8.6 Hz, 2H), 4.91 (dq,J=9.1, 6.4 Hz, 1H), 4.55 (ddd, J=10.9, 8.4, 7.0 Hz, 1H), 3.88 (s, 3H),3.81 (t, J=6.6 Hz, 2H), 3.78 (s, 3H), 3.57 (dd, J=9.7, 7.0 Hz, 1H), 3.44(dd, J=9.7, 6.8 Hz, 1H), 3.41 (s, 3H), 3.15 (t, J=9.0 Hz, 1H), 3.07 (dd,J=13.4, 3.3 Hz, 1H), 2.98 (t, J=6.6 Hz, 2H), 2.35-2.20 (m, 2H),1.87-1.77 (m, 1H), 1.61-1.47 (m, 2H), 1.48-1.37 (m, 1H), 1.45 (d, J=6.4Hz, 3H), 1.22-1.05 (m, 2H), 0.90-0.79 (m, 1H), 0.63-0.49 (m, 2H),0.29-0.14 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ 172.61, 169.39, 162.32,159.40, 157.82, 146.76, 141.45, 137.29, 132.66, 129.73, 113.77, 109.78,83.79, 78.71, 75.22, 67.58, 58.78, 56.30, 55.22, 51.47, 46.17, 35.92,34.62, 33.89, 26.55, 18.73, 18.08, 11.18, 3.16, 3.00; HRMS-ESI (m/z)([M]⁺) calcd for C₃₂H₄₂N₂O₉, 598.2890. found, 598.2914.

Example 12 Preparation of((2-(((3S,7R,8R,9S)-7-(cyclopentylmethyl)-8-(cyclopropylmethoxy)-9-methyl-2-oxooxonan-3-yl)carbamoyl)-4-methoxypyridin-3-yl)oxy)methylisobutyrate (F154)

To a mixture ofN-((3S,7R,8R,9S)-7-(cyclopentylmethyl)-8-(cyclopropylmethoxy)-9-methyl-2-oxooxonan-3-yl)-3-hydroxy-4-methoxypicolinamide(60 mg, 0.126 mmol) and K₂CO₃ (34.9 mg, 0.253 mmol) in acetone (1 mL)was added chloromethyl isobutyrate (34.5 mg, 0.253 mmol) and thereaction was heated to 60° C. After TLC analysis indicated fullconsumption of the picolinamide starting material, the mixture wasconcentrated under a stream of N₂ and the residue purified by columnchromatography on SiO₂ (gradient, EtOAc/hexanes) to yield the titlecompound as a colorless semi-solid (60.4 mg, 83%): IR (thin film) 3381,2942, 1745, 1678, 1506, 974 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 8.38 (d,J=8.2 Hz, 1H), 8.27 (d, J=5.3 Hz, 1H), 6.93 (d, J=5.4 Hz, 1H), 5.81-5.61(m, 2H), 4.89 (dd, J=9.2, 6.3 Hz, 1H), 4.57 (dt, J=11.0, 7.5 Hz, 1H),3.89 (s, 3H), 3.50 (dd, J=9.6, 7.0 Hz, 1H), 3.36 (dd, J=9.6, 6.9 Hz,1H), 3.01 (t, J=9.0 Hz, 1H), 2.54 (p, J=7.0 Hz, 1H), 2.36 (dd, J=13.1,6.8 Hz, 1H), 1.92-1.43 (m, 15H), 1.42 (d, J=6.5 Hz, 2H), 1.35-1.19 (m,2H), 1.14 (d, J=7.0 Hz, 3H), 1.17-0.92 (m, 5H), 0.62-0.48 (m, 2H),0.29-0.17 (m, 2H); HRMS-ESI (m/z) ([M]⁺) calcd for C₃₁H₄₆N₂O₈, 574.3254.found, 574.3262.

Example 13 Preparation of((4-methoxy-2-(((3S,7R,8R,9S)-9-methyl-7-(4-methyl-benzyl)-2-oxo-8-(4,4,4-trifluorobutoxy)oxonan-3-yl)carbamoyl)pyridin-3-yl)oxy)methyl2-ethoxyacetate (F190)

To a 25 mL screw top vial were added3-hydroxy-4-methoxy-N-((3S,7R,8R,9S)-9-methyl-7-(4-methylbenzyl)-2-oxo-8-(4,4,4-trifluorobutoxy)oxonan-3-yl)picolinamide(87.9 mg, 0.159 mmol), Na₂CO₃ (33.8 mg, 0.319 mmol), NaI (6.3 mg, 0.264mmol), anhydrous acetone (2 mL), and chloromethyl 2-ethoxyacetate (40.8mg, 1.68 mmol), and the resulting mixture was warmed to 40° C. andstirred for 17 h. The reaction was cooled to room temperature,concentrated under a stream of nitrogen, and purified by columnchromatography on SiO₂ (2→40% acetone/hexanes) to provide the titlecompound as a colorless oil (58.8 mg, 52%): ¹H NMR (400 MHz, CDCl₃) δ8.29 (d, J=8.1 Hz, 1H), 8.25 (d, J=5.4 Hz, 1H), 7.09 (d, J=7.9 Hz, 2H),7.03 (d, J=8.0 Hz, 2H), 6.93 (d, J=5.4 Hz, 1H), 5.80 (s, 2H), 4.89 (dq,J=9.1, 6.4 Hz, 1H), 4.55 (dt, J=10.9, 7.4 Hz, 1H), 4.08 (s, 2H), 3.88(s, 3H), 3.80 (dt, J=8.9, 6.1 Hz, 1H), 3.64-3.54 (m, 3H), 3.17 (t, J=9.0Hz, 1H), 2.96 (dd, J=13.3, 3.4 Hz, 1H), 2.40-2.13 (m, 7H), 1.92-1.76 (m,3H), 1.65-1.37 (m, 6H), 1.30-1.14 (m, 4H), 0.93-0.80 (m, 1H); ¹³C NMR(101 MHz, CDCl₃) δ 172.62, 169.97, 162.83, 160.09, 145.73, 143.81,142.18, 137.20, 135.41, 129.02, 128.58, 131.42-122.86 (m), 109.65,89.44, 84.20, 74.83, 71.60, 67.71, 67.10, 56.15, 51.69, 45.80, 36.42,33.56, 30.73 (q, J=29.0 Hz), 26.62, 23.01 (q, J=3.1 Hz), 20.93, 18.75,18.05, 14.94; ¹⁹F NMR (376 MHz, CDCl₃) δ−66.35, ESIMS: m/z 669 ([M+H]⁺).

Example 14 Preparation of (S)-benzyl5-((2R,3R)-2-((S)-1-(benzyloxy)ethyl)-tetrahydrofuran-3-yl)-2-((tert-butoxycarbonyl)amino)pentanoate

To a solution of (2S,6R,7R,8S)-benzyl8-(benzyloxy)-2-((tert-butoxycarbonyl)amino)-7-(cyclopropylmethoxy)-6-(2-hydroxyethyl)nonanoate(570 mg, 0.976 mmol) in anhydrous CH₂Cl₂ (10 mL) at 0° C. were addedCBr₄ (389 mg, 1.172 mmol) and triphenylphosphine (333 mg, 1.269 mmol).The resulting solution was stirred for 6 h, at which time UPLC-MS showed˜50% conversion to the desired product. The reaction was allowed to warmto room temperature and stirred for 3 d. The mixture was concentratedand purified by column chromatography on SiO₂ (2→25% acetone/hexanes) toprovide the title compound as a clear, colorless oil (399.6 mg, 80%): ¹HNMR (400 MHz, CDCl₃) δ 7.39-7.28 (m, 9H), 7.28-7.21 (m, 1H), 5.20 (d,J=12.3 Hz, 1H), 5.11 (d, J=12.3 Hz, 1H), 5.00 (d, J=8.1 Hz, 1H), 4.62(d, J=11.9 Hz, 1H), 4.49 (d, J=11.9 Hz, 1H), 4.42-4.26 (m, 1H), 3.78(dd, J=8.3, 4.8 Hz, 2H), 3.56-3.40 (m, 2H), 1.96 (ddd, J=14.2, 10.0, 7.2Hz, 2H), 1.76 (dd, J=8.8, 4.7 Hz, 1H), 1.68-1.55 (m, 1H), 1.49 (dd,J=7.8, 3.6 Hz, 2H), 1.44 (s, 9H), 1.39-1.33 (m, 1H), 1.32-1.21 (m, 2H),1.18 (d, J=6.1 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 172.71, 155.37,138.92, 135.43, 128.60, 128.43, 128.32, 128.29, 127.59, 127.41, 87.07,79.88, 71.09, 67.77, 66.97, 53.39, 40.81, 33.92, 32.84, 32.66, 28.33,24.04, 16.01; ESIMS m/z 412.3 ([M+H]⁺) for M-BOC.

Example 15 Step 1: Preparation of (phenylthio)methyl 2-ethoxyacetate

To a mixture of Cs₂CO₃ (29.5 g, 91 mmol) in DMF (150 mL) at 0° C. wasadded 2-ethoxyacetic acid (18.0 mL, 191 mmol), and the resulting mixturewas heated at 70° C. for 30 min. The reaction was cooled to 0° C.,chloromethyl phenylsulfide (10.56 mL, 79 mmol) was added, and thereaction was heated at 70° C. for 90 min. The mixture was cooled to roomtemperature, and then 0° C., before diluting with H₂O (200 mL; anexotherm was observed). The reaction mixture was divided into two equalportions and one portion was further diluted with water (400 mL) andextracted with Et₂O (200 mL×2, 100 mL×1). The combined organic extractswere diluted with hexane (100 mL) and washed successively with 1.0 Maqueous NaOH (100 mL) and brine (2×200 mL), dried over anhydrous MgSO₄,filtered, and concentrated. The second portion of the reaction mixturefrom above was processed in an identical fashion and the two lots werecombined and concentrated in vacuo to afford the title compound as ayellow oil (12.28 g, 97%): ¹H NMR (400 MHz, CDCl₃) δ 7.48-7.41 (m, 2H),7.31 (ddd, J=12.6, 7.9, 6.3 Hz, 3H), 5.51 (s, 2H), 4.11 (s, 2H), 3.59(q, J=7.0 Hz, 2H), 1.24 (t, J=7.0 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ170.00, 134.35, 130.53, 129.16, 127.55, 68.46, 68.10, 67.32, 14.99;ESIMS: m/z 226 ([M]⁺).

Example 15 Step 2: Preparation of chloromethyl 2-ethoxyacetate

To a solution of (phenylthio)methyl 2-ethoxyacetate (17.28 g, 76 mmol)in CH₂Cl₂ (200 mL) at 0° C. was added a solution of sulfuryl chloride(7.36 mL, 92 mmol) in CH₂Cl₂ (50 mL) over a period of 15 min, and thereaction was stirred at room temperature for 90 min. The reaction wasagain cooled to 0° C. and treated with a second portion of sulfurylchloride (7.36 mL, 92 mmol) in CH₂Cl₂ (50 mL) over a period of 15 min.The reaction was then warmed to 30° C., stirred for 1 hour, and thencooled back to 0° C. A solution of cyclohexene (24.5 mL, 242 mmol) inCH₂Cl₂ (50 mL) was added over a period of 10 min, during which gasevolution was observed. The reaction was stirred at room temperature for90 min, stored at −20° C. overnight, and purified by vacuum distillationto give the target compound as a slightly yellow oil (11.33 g, 97%): by58° C. at 6.8 mm Hg; ¹H NMR (400 MHz, CDCl₃) δ 5.77 (s, 2H), 4.16 (s,2H), 3.62 (q, J=7.0 Hz, 2H), 1.27 (t, J=7.0 Hz, 3H); ¹³C NMR (101 MHz,CDCl₃) δ 168.81, 68.59, 67.77, 67.48, 14.96.

Example 16 Preparation ofN-((3S,7R,8R,9S)-7-(cyclohexylmethyl)-8-(cyclopropyl-methoxy)-9-methyl-2-oxooxonan-3-yl)-3-hydroxy-4-methoxypicolinamide(F9)

A high pressure reactor equipped with a stir bar was charged with asolution ofN-((3S,7R,8R,9S)-8-(cyclopropylmethoxy)-7-(4-fluorobenzyl)-9-methyl-2-oxooxonan-3-yl)-3-hydroxy-4-methoxypicolinamide(230 mg, 0.459 mmol) in THF (7 mL) and 5% rhodium on carbon (56.8 mg,0.028 mmol). After the reactor was sealed and purged with H₂ (4×), thereaction was charged to ˜600 psi of H₂ at room temperature. The reactorwas warmed to 70° C. and stirred for 29 h, cooled to room temperature,and the reaction mixture was filtered through a Celite® pad. Thefiltrate was concentrated and purified by column chromatography on SiO₂(gradient, hexanes/ethyl acetate) to furnish the title product as awhite solid (60.8 mg, 27%): ¹H NMR (400 MHz, CDCl₃) δ 12.11 (d, J=0.6Hz, 1H), 8.49 (d, J=8.2 Hz, 1H), 7.99 (d, J=5.2 Hz, 1H), 6.87 (d, J=5.2Hz, 1H), 4.95-4.84 (m, 1H), 4.55 (ddd, J=10.7, 8.2, 7.0 Hz, 1H), 3.94(s, 3H), 3.49 (dd, J=9.6, 7.0 Hz, 1H), 3.37 (dd, J=9.6, 6.8 Hz, 1H),3.01 (t, J=8.8 Hz, 1H), 2.39-2.28 (m, 1H), 1.78-1.46 (m, 10H), 1.45 (d,J=7.0 Hz, 3H), 1.41-0.71 (m, 10H), 0.59-0.52 (m, 2H), 0.26-0.18 (m, 2H);¹³C NMR (101 MHz, CDCl₃) δ 172.21, 168.62, 155.31, 148.69, 140.51,130.42, 109.44, 84.33, 78.51, 75.66, 56.05, 51.49, 40.09, 38.30, 35.05,34.59, 33.63, 32.34, 27.44, 26.68, 26.48, 26.15, 18.77, 18.10, 11.14,3.16, 2.94; ESIMS m/z 489.3 ([M+H]⁺).

Example A: Evaluation of Fungicidal Activity: Leaf Blotch of Wheat(Mycosphaerella graminicola; Anamorph: Septoria tritici; Bayer codeSEPTTR):

Technical grades of materials were dissolved in acetone, which were thenmixed with nine volumes of water containing 110 ppm Triton X-100. Thefungicide solutions were applied onto wheat seedlings using an automatedbooth sprayer to run-off. All sprayed plants were allowed to air dryprior to further handling. All fungicides were evaluated using theaforementioned method for their activity vs. all target diseases. Wheatleaf blotch and brown rust activity were also evaluated using trackspray applications, in which case the fungicides were formulated as ECformulations, containing 0.1% Trycol 5941 in the spray solutions.

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%mineral soil/50% soil-less Metro mix until the first leaf was fullyemerged, with 7-10 seedlings per pot. These plants were inoculated withan aqueous spore suspension of Septoria tritici either prior to or afterfungicide treatments. After inoculation the plants were kept in 100%relative humidity (one day in a dark dew chamber followed by two tothree days in a lighted dew chamber at 20° C.) to permit spores togerminate and infect the leaf. The plants were then transferred to agreenhouse set at 20° C. for disease to develop. When disease symptomswere fully expressed on the 1^(st) leaves of untreated plants, infectionlevels were assessed on a scale of 0 to 100 percent disease severity.Percent disease control was calculated using the ratio of diseaseseverity on treated plants relative to untreated plants.

Example B: Evaluation of Fungicidal Activity: Wheat Brown Rust (Pucciniatriticina; Synonym: Puccinia recondite f sp. tritici; Bayer codePUCCRT):

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%mineral soil/50% soil-less Metro mix until the first leaf was fullyemerged, with 7-10 seedlings per pot. These plants were inoculated withan aqueous spore suspension of Puccinia triticina either prior to orafter fungicide treatments. After inoculation the plants were kept in adark dew room at 22° C. with 100% relative humidity overnight to permitspores to germinate and infect the leaf. The plants were thentransferred to a greenhouse set at 24° C. for disease to develop.Fungicide formulation, application and disease assessment followed theprocedures as described in the Example A.

Example C: Evaluation of Fungicidal Activity: Wheat Glume Blotch(Leptosphaeria nodorum; Bayer code LEPTNO):

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%mineral soil/50% soil-less Metro mix until the first leaf was fullyemerged, with 7-10 seedlings per pot. These plants were inoculated withan aqueous spore suspension of Leptosphaeria nodorum 24 hr afterfungicide treatments. After inoculation the plants were kept in 100%relative humidity (one day in a dark dew chamber followed by two days ina lighted dew chamber at 20° C.) to permit spores to germinate andinfect the leaf. The plants were then transferred to a greenhouse set at20° C. for disease to develop. Fungicide formulation, application anddisease assessment followed the procedures as described in the ExampleA.

Example D: Evaluation of Fungicidal Activity: Apple Scab (Venturiainaequalis; Bayer code VENTIN):

Apple seedlings (variety McIntosh) were grown in soil-less Metro mix,with one plant per pot. Seedlings with two expanding young leaves at thetop (older leaves at bottom of the plants were trimmed) were used in thetest. Plants were inoculated with a spore suspension of Venturiainaequalis 24 hr after fungicide treatment and kept in a 22° C. dewchamber with 100% RH for 48 hr, and then moved to a greenhouse set at20° C. for disease to develop. Fungicide formulation, application anddisease assessment on the sprayed leaves followed the procedures asdescribed in the Example A.

Example E: Evaluation of Fungicidal Activity: Grape Powdery Mildew(Uncinula necator; Bayer code UNCINE):

Grape seedlings (variety Carignane) were grown in soil-less Metro mix,with one plant per pot, and used in the test when approximately onemonth old. Plants were inoculated 24 hr after fungicide treatment byshaking spores from infected leaves over test plants. Plants weremaintained in a greenhouse set at 20° C. until disease was fullydeveloped. Fungicide formulation, application and disease assessment onthe sprayed leaves followed the procedures as described in the ExampleA.

Example F: Evaluation of Fungicidal Activity: Powdery Mildew of Cucumber(Erysiphe cichoracearum; Bayer code ERYSCI):

Cucumber seedlings (variety Bush Pickle) were grown in soil-less Metromix, with one plant per pot, and used in the test when 12 to 14 daysold. Plants were inoculated with a spore suspension 24 hr followingfungicide treatments. After inoculation the plants remained in thegreenhouse set at 20° C. until disease was fully expressed. Fungicideformulation, application and disease assessment on the sprayed leavesfollowed the procedures as described in the Example A.

Example G: Evaluation of Fungicidal Activity: Leaf Spot of Sugar Beets(Cercospora beticola; Bayer code CERCBE):

Sugar beet plants (variety HH88) were grown in soil-less Metro mix andtrimmed regularly to maintain a uniform plant size prior to test. Plantswere inoculated with a spore suspension 24 hr after fungicidetreatments. Inoculated plants were kept in a dew chamber at 22° C. for48 hr then incubated in a greenhouse set at 24° C. under a clear plastichood with bottom ventilation until disease symptoms were fullyexpressed. Fungicide formulation, application and disease assessment onthe sprayed leaves followed the procedures as described in the ExampleA.

Example H: Evaluation of Fungicidal Activity: Asian Soybean Rust(Phakopsora pachyrhizi; Bayer code PHAKPA):

Technical grades of materials were dissolved in acetone, which were thenmixed with nine volumes of water containing 0.011% Tween 20. Thefungicide solutions were applied onto soybean seedlings using anautomated booth sprayer to run-off. All sprayed plants were allowed toair dry prior to further handling.

Soybean plants (variety Williams 82) were grown in soil-less Metro mix,with one plant per pot. Two weeks old seedlings were used for testing.Plants were inoculated either 3 days prior to or 1 day after fungicidetreatments. Plants were incubated for 24 h in a dark dew room at 22° C.and 100% RH then transferred to a growth room at 23° C. for disease todevelop. Disease severity was assessed on the sprayed leaves.

Example I: Evaluation of Fungicidal Activity: Wheat Powdery Mildew(Blumeria graminis f. sp. tritici; Synonym: Erysiphe graminis f. sp.tritici; Bayer code ERYSGT):

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%mineral soil/50% soil-less Metro mix until the first leaf was fullyemerged, with 7-10 seedlings per pot. These plants were inoculated bydusting with infected stock plants 24 hr after fungicide treatments.After inoculation the plants were kept in a greenhouse set at 20° C. fordisease to develop. Fungicide formulation, application and diseaseassessment on the sprayed leaves followed the procedures as described inthe Example A.

Example J: Evaluation of Fungicidal Activity: Barley Powdery Mildew(Blumeria graminis f. sp. hordei; Synonym: Erysiphe graminis f. sp.hordei; Bayer code ERYSGH):

Barley seedlings (variety Harrington) were propagated in soil-less Metromix, with each pot having 8 to 12 plants, and used in the test whenfirst leaf was fully emerged. Test plants were inoculated by dustingwith infected stock plants 24 hr after fungicide treatments. Afterinoculation the plants were kept in a greenhouse set at 20° C. fordisease to develop. Fungicide formulation, application and diseaseassessment on the sprayed leaves followed the procedures as described inthe Example A.

Example K: Evaluation of Fungicidal Activity: Barley Scald(Rhyncosporium secalis; Bayer code RHYNSE):

Barley seedlings (variety Harrington) were propagated in soil-less Metromix, with each pot having 8 to 12 plants, and used in the test whenfirst leaf was fully emerged. Test plants were inoculated by an aqueousspore suspension of Rhyncosporium secalis 24 hr after fungicidetreatments. After inoculation the plants were kept in a dew room at 20°C. with 100% relative humidity for 48 hr. The plants were thentransferred to a greenhouse set at 20° C. for disease to develop.Fungicide formulation, application and disease assessment on the sprayedleaves followed the procedures as described in the Example A.

Example L: Evaluation of Fungicidal Activity: Rice Blast (Magnaporthegrisea; Anamorph: Pyricularia oryzae; Bayer code PYRIOR):

Rice seedlings (variety Japonica) were propagated in soil-less Metromix, with each pot having 8 to 14 plants, and used in the test when 12to 14 days old. Test plants were inoculated with an aqueous sporesuspension of Pyricularia oryzae 24 hr after fungicide treatments. Afterinoculation the plants were kept in a dew room at 22° C. with 100%relative humidity for 48 hr to permit spores to germinate and infect theleaf. The plants were then transferred to a greenhouse set at 24° C. fordisease to develop. Fungicide formulation, application and diseaseassessment on the sprayed leaves followed the procedures as described inthe Example A.

Example M: Evaluation of Fungicidal Activity: Tomato Early Blight(Alternaria solani; Bayer code ALTESO):

Tomato plants (variety Outdoor girl) were propagated in soil-less Metromix, with each pot having one plant, and used when 12 to 14 days old.Test plants were inoculated with an aqueous spore suspension ofAlternaria solani 24 hr after fungicide treatments. After inoculationthe plants were kept in 100% relative humidity (one day in a dark dewchamber followed by two to three days in a lighted dew chamber at 20°C.). to permit spores to germinate and infect the leaf. The plants werethen transferred to a growth room at 22° C. for disease to develop.Fungicide formulation, application and disease assessment on the sprayedleaves followed the procedures as described in the Example A.

Example N: Evaluation of Fungicidal Activity: Cucumber Anthracnose(Glomerella lagenarium; Anamorph: Colletotrichum lagenarium; Bayer codeCOLLLA):

Cucumber seedlings (variety Bush Pickle) were propagated in soil-lessMetro mix, with each pot having one plant, and used in the test when 12to 14 days old. Test plants were inoculated with an aqueous sporesuspension of Colletotrichum lagenarium 24 hr after fungicidetreatments. After inoculation the plants were kept in a dew room at 22°C. with 100% relative humidity for 48 hr to permit spores to germinateand infect the leaf. The plants were then transferred to a growth roomset at 22° C. for disease to develop. Fungicide formulation, applicationand disease assessment on the sprayed leaves followed the procedures asdescribed in the Example A.

TABLE 1 Compound Structure and Appearance Prepared According Compound ToNumber Structure Example Appearance F1

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 7; Step 2a; Example 8, Steps 1, 2 Colorless Solid F2

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2 White Solid F3

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Steps 1, 2 White SolidF4

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2 White Solid F5

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2 White Solid F6

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2 Pale Yellow Sticky SolidF7

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 6; Example 8, Steps 1, 2 Colorless Thick Oil F8

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5; Example 8, Steps 1, 2 Sticky Colorless Oil F9

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2 WhiteSolid F10

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2 WhiteSolid F11

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2 ColorlessSolid F12

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Step 1; Example 8, Steps 1, 2 White Solid F13

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2 White Solid F14

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2 Colorless Solid F15

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2b- 1, 2b-2; Example 8, Steps 1, 2 White Solid F16

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5; Example 8, Steps 1, 2 White Solid F17

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5; Example 8, Steps 1, 2 White Solid F18

Example 1, Steps 1, 2b, 3, 4, 5b, 6, Example 8, Steps 1, 2 White SolidF19

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6, Example 8, Steps 1, 2 Thick OilF20

Example 1, Steps 1, 2a, 3, 4, 5b, 6, Example 8, Steps 1, 2 White SolidF21

Example 1, Steps 1, 2b, 3, 4, 5b, 6; Example 2, Step 1b; Example 8,Steps 1, 2 White Solid F22

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6, 5b; Example 2, Step 1b; Example3 Steps 1, 2a, Example 8, Steps 1, 2 White Solid F23

Example 1, Steps 1, 2b, 3, 4, 5b, 6, Example 8, Steps 1, 2 White SolidF24

Example 1, Steps 1, 2b, 3, 4, 5b, 6, Example 8, Steps 1, 2 Foam F25

Example 1, Steps 1, 2b, 3, 4, 5b, 6, Example 8, Steps 1, 2; Example 16White Solid F26

Example 8, Steps 1, 2 Colorless Semi- Solid F27

Example 8, Steps 1, 2 White Solid F28

Example 8, Steps 1, 2 Colorless Oil F29

Example 8, Steps 1, 2 White Solid F30

Example 8, Steps 1, 2 White Solid F31

Example 8, Steps 1, 2 White Solid F32

Example 8, Steps 1, 2 Colorless Semi Solid F33

Example 8, Steps 1, 2 Colorless Semi- Solid F34

Example 8, Steps 1, 2 White Solid F35

Example 8, Steps 1, 2 Light Yellow Solid F36

Example 8, Steps 1, 2 White Solid F37

Example 8, Steps 1, 2 White Solid F38

Example 8 Step 1 Step 2 White Solid F39

Example 8, Steps 1, 2 White Solid F40

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6, 5b; Example 2, Step 1b; Example8, Steps 1, 2 Colorless Thick Oil F41

Example 8 White Solid F42

Example 8 Colorless Oil F43

Example 8, Step 2 White Solid F44

Example 8, Step 2 White Solid F45

Example 8, Step 2 White Solid F46

Example 8, Step 2 White Solid F47

Example 8, Step 2 White Solid F48

Example 8, Step 2 White Solid F49

Example 8 White Solid F50

Example 8, Step 2 White Solid F51

Example 8, Step 2 Hard White Foam F52

Example 8 White Solid F53

Example 8, Step 2 White Solid F54

Example 8, Step 2 Sticky Glassy Solid F55

Example 8 White Solid F56

Example 8 Colorless Oil F57

Example 8, Step 2 White Solid F58

Example 8, Step 2 White Solid F59

Example 8 White Solid F60

Example 8 White Solid F61

Example 8, Step 2 Yellow Solid F62

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 7; Step 2a; Example 8, Steps 1, 2; Example 10 Yellow Solid F63

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Steps 1, 2; Example 10Yellow Oil F64

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 10 Yellow SolidF65

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 10 CrystallineYellow Solid F66

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 6; Example 8, Steps 1, 2; Example 10 Yellow Solid F67

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example10 Yellow Oil F68

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example10 Yellow Oil F69

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2b- 1, 2b-2; Example 8, Steps 1, 2; Example 10 PaleYellow Solid F70

Example 10 Colorless Thick Oil F71

Example 10 Colorless Oil F72

Example 10 White Solid F73

Example 10 Sticky Yellow Semi Solid F74

Example 10 Sticky White Solid F75

Example 10 White Solid F76

Example 10 White Glassy Solid F77

Example 10 White Solid F78

Example 10 White Solid F79

Example 10 White Solid F80

Example 10 Hard White Foam F81

Example 10 White Solid F82

Example 10 White Solid F83

Example 10 White Solid F84

Example 10 White Solid F85

Example 10 White Solid F86

Example 10 White Solid F87

Example 10 White Foam F88

Example 10 White Foam F89

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 7; Step 2a; Example 8, Steps 1, 2; Example 9 Colorless Solid F90

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Colorless OilF91

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Steps 1, 2; Example 9Colorless Oil F92

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Thick ColorlessOil F93

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Pale Yellow OilF94

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Pale YellowSticky Solid F95

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 6; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F96

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5; Example 8, Steps 1, 2; Example 9 Colorless Oil F97

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example16; Example 9 Pale Yellow Oil F98

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example9 Pale Yellow Oil F99

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example9 Pale Yellow Oil F100

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Step 1; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F101

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Pale Yellow OilF102

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 9 Pale Yellow OilF103

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2b- 1, 2b-2; Example 8, Steps 1, 2; Example 9 PaleYellow Oil F104

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5; Example 8, Steps 1, 2; Example 9 Colorless Oil F105

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5; Example 8, Steps 1, 2; Example 9 Pale Yellow Oil F106

Example 9 Thick Oil F107

Example 9 Sticky Oil F108

Example 9 White Solid F109

Example 9 Sticky White Foam F110

Example 9 White Foam F111

Example 9 White Foam F112

Example 9 White Foam F113

Example 9 Colorless Thick Oil F114

Example 9 Colorless Semi- Solid F115

Example 9 Yellow Oil F116

Example 9 Sticky White Solid F117

Example 9 Colorless Semi Solid F118

Example 9 Colorless Semi Solid F119

Example 9 Light Yellow Oil F120

Example 9 Colorless Solid F121

Example 9 Colorless Oil F122

Example 9 Colorless Oil F123

Example 9 Colorless Oil F124

Example 9 White Glassy Solid F125

Example 9 Solid F126

Example 9 White Oil F127

Example 9 White Solid F128

Example 9 White Solid F129

Example 9 White Solid F130

Example 9 White Solid F131

Example 9 Sticky Yellow Solid F132

Example 9 Sticky Oil F133

Example 9 Sticky Solid F134

Example 9 White Solid F135

Example 9 White Solid F136

Example 9 Yellow Solid F137

Example 9 Colorless Oil F138

Example 9 White Solid F139

Example 9 Colorless Oil F140

Example 9 Colorless Oil F141

Example 9 White Solid F142

Example 9 White Solid F143

Example 9 White Solid F144

Example 9 Off White Solid F145

Example 9 Off White Solid F146

Example 9 White Solid F147

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 7; Step 2a; Example 8, Steps 1, 2; Example 12 Colorless Oil F148

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 12 Pale YellowOil F149

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Steps 1, 2; Example 12Yellow Oil F150

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 12 Sticky YellowSolid F151

Example 12 White Solid F152

Example 12 Thick Oil F153

Example 11 Colorless Oil F154

Example 12 Colorless Semi Solid F155

Example 12 White Glassy Solid F156

Example 12 Colorless Oil F157

Example 12 White Solid F158

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 7; Step 2a; Example 8, Steps 1, 2; Example 13 Colorless Oil F159

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 13 White StickySolid F160

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Steps 1, 2; Example 13Colorless Sticky Solid F161

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 13 Colorless OilF162

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a; Example 8, Steps 1, 2; Example 13 Yellow OilF163

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 6; Example 8, Steps 1, 2; Example 13 Colorless Oil F164

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example13 Colorless Oil F165

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6; Example 8, Steps 1, 2; Example13 Colorless Solid F166

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Step 1; Example 8, Steps 1, 2; Example 13 Colorless Oil F167

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 13 Colorless OilF168

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Steps 1, 2; Example 13 Colorless OilF169

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2b- 1, 2b-2; Example 8, Steps 1, 2; Example 13Colorless Oil F170

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5; Example 8, Steps 1, 2; Example 13 Pale Yellow Oil F171

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5; Example 8, Steps 1, 2; Example 13 White Solid F172

Example 13 Colorless Thick Oil F173

Example 13 Colorless Thick Oil F174

Example 13 White Foam F175

Example 13 Colorless Thick Oil F176

Example 13 Colorless Oil F177

Example 13 Sticky White Solid F178

Example 13 Colorless Semi- Solid F179

Example 13 Colorless Oil F180

Example 13 White Solid F181

Example 13 Sticky Solid F182

Example 13 White Solid F183

Example 13 White Solid F184

Example 13 Colorless Film F185

Example 13 Colorless Film F186

Example 13 Colorless Film F187

Example 13 Colorless Oil F188

Example 13 Colorless Film F189

Example 13 White Solid F190

Example 13 Colorless Oil F191

Example 13 Colorless Oil F192

Example 13 White Solid F193

Example 13 White Solid F194

Example 11 Colorless Semi Solid F195

Example 11 Colorless Semi- Solid F196

Example 10 White Solid F197

Example 11 White Foam F198

Example 11 White Foam F199

Example 1, Steps 1, 2a, 3, 5b, 5c, 6 White Solid F200

Example 1, Steps 1, 2b, 3, 5b, 5c, 6 Colorless Oil F201

Example 1, Steps 1, 2b, 3, 5b, 5c, 6 Colorless Solid F202

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a Colorless Oil F203

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a White Solid F204

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a Colorless Oil F205

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 6 White Solid F206

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5 Colorless Thick Oil F207

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6 Colorless Foam F208

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6 Colorless Solid F209

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Step 1 Pale Yellow Oil F210

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a Colorless Oil F211

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a Colorless Oil F212

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2b- 1, 2b-2 White Solid F213

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5 Colorless Oil F214

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5 Colorless Oil F215

Example 1, Steps 1, 2a, 3, 4, 5a, 5c, 6 Colorless Semi Solid F216

Example 1, Steps 1, 2a, 3, 4, 5a, 5c, 6 White Foam F217

Example 1, Steps 1, 2c, 3, 4, 5a, 5c, 6; Example 2, Step 1a- 1, 1a-2;Example 5 Yellow Solid F218

Example 1, Steps 1, 2c, 3, 4, 5a, 5c, 6; Example 2, Steps 1a- 1, 1a-2;Example 4 Colorless Oil F219

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6 Thick Colorless Oil F220

Example 1, Steps 1, 2c, 3, 4, 5a, 5c, 6; Example 2, Steps 1, 2; Example3 Colorless Oil F221

Example 1, Steps 1, 2c, 3, 4, 5a, 5c, 6; Example 2, Steps 1, 2; Example3 Colorless Oil F222

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6 Colorless Oil F223

Example 1, Step 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Step 1, 2; Example 5Yellow Solid F224

Example 1, Step 1 2a, 3, 4, 5a, 5b, 6 White Solid F225

Example 1, Step 1 2a, 3, 4, 5a, 5b, 6 Thick Oil F226

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6, 5b; Example 2, Step 1b WhiteSolid F227

Example 1, Steps 1, 2b, 3, 4, 5b, 6 Colorless Oil F229

Example 1 White Solid F230

Example 2, Step 1b White Solid F231

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6 White Solid F232

Example 1, Steps 1, 2b, 3, 4, 5b, 6; Example 2, Step 1b White Solid F233

Example 1, Steps 1, 2b, 3, 4, 5b, 6 White Solid F234

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6 Oily White Solid F235

Example 7, Step 2e — F236

Example 1 White Solid F237

Example 1, Steps 1, 2b, 3, 4, 5b, 6 White Solid F238

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6, 5b; Example 2, Step 1b; Example3 Steps 1, 2a, Colorless Oil F239

Example 1, Steps 1, 2b, 3, 4, 5a, 5c, 6 Colorless Semi Solid F240

Example 7, Step 2a — F241

Example 1, Steps 1, 2a, 3, 4, 5b, 6 White Foam F242

Example 7, Step 2b — F243

Example 7, Step 2b White Solid F244

Example 1 White Solid F245

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 7, Step 2a Colorless Sticky Oil F246

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a Colorless Oil F247

Example 7, Step 2d-2 — F248

Example 1 Colorless Oil F249

Example 7, Step 2d-1 White Foam F250

Example 7, Step 2d-2 White Solid F251

Example 1, Step 6 Oil F253

Example 2, Step 1b Colorless Oil F254

Example 2, Step 1a-1, 1a-2 Yellow Solid F255

Example 3 Colorless Oil F256

Example 3 Colorless Oil F257

Example 1, Step 6 Sticky Oil F258

Example 1, Step 6 White Solid F259

Example 7, Step 2f-2 Orange Solid F260

Example 5 White Solid F261

Example 3 Colorless Oil F262

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 7; Step 2a; Example 8, Step 1 White Solid F263

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a; Example 8, Step 1 White Solid F264

Example 1, Steps 1, 2b, 3, 5b, 5c, 6; Example 8, Step 1 White Solid F265

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a; Example 8, Step 1 White Solid F266

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a; Example 8, Step 1 White Solid F267

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3; Steps 1, 2a; Example 8, Step 1 Pale Yellow Thick Oil F268

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 6; Example 8, Step 1 White Solid F269

Example 1, Steps 1, 2c, 3, 4, 5c, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5; Example 8, Step 1 White Sticky Solid F271

Example 1, Steps 1, 2b, 3, 4, 5a, 5b, 6; Example 8, Step 1 White SolidF272

Example 1, Steps 1, 2a, 3, 4, 5a, 5b, 6; Example 8, Step 1 ColorlessSolid F273

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Step 1; Example 8, Step 1 Off- White Solid F274

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Step 1 White Solid F275

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2a; Example 8, Step 1 White Solid F276

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 3, Steps 1, 2b- 1, 2b-2; Example 8, Step 1 White Solid F277

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5; Example 8, Step 1 White Solid F278

Example 1, Steps 1, 2c, 3, 4, 5a, 5b, 6; Example 2, Steps 1a- 1, 1a-2;Example 5; Example 8, Step 1 White Solid F279

Example 8 Step 1 White Solid F280

Example 8 Step 1 White Solid F281

Example 8 Step 1 White Solid F282

Example 8 Step 1 White Solid F283

Example 8 Step 1 White Solid F284

Example 8 Step 1 White Solid F285

Example 8 Step 1 White Solid F287

Example 8, Step 1 White Solid F288

Example 8, Step 1 White Solid F289

Example 8, Step 1 White Solid F290

Example 8, Step 1 White Solid F291

Example 8, Step 1 White Solid F292

Example 8, Step 1 White Solid F293

Example 8, Step 1 Colorless Semi- Solid F294

Example 8, Step 1 Colorless Semi- Solid F295

Example 8, Step 1 White Solid F296

Example 8, Step 1 Orange Solid F297

Example 8, Step 1 White Solid F298

Example 8, Step 1 White Solid F299

Example 8, Step 1 White Solid F300

Example 8, Step 1 White Solid F301

Example 8, Step 1 White Solid F302

Example 8 White Solid F303

Example 8, Step 1 White Solid F304

Example 8, Step 1 White Solid F305

Example 8, Step 1 White Solid F306

Example 8, Step 1 — F307

Example 8, Step 1 Yellow Solid F308

Example 8 Beige Solid F309

Example 8, Step 1 White Solid F310

Example 8, Step 1 White Solid F311

Example 8 White Solid F312

Example 8, Step 1 White Solid F313

Example 8, Step 1 — F314

Example 8, Step 1 White Solid F315

Example 8, Step 1 — F316

Example 8 Tacky White Solid F317

Example 8 White Solid F318

Example 8, Step 1 White Solid F319

Example 8, Step 1 White Solid F320

Example 8, Step 1 — F321

Example 8 White Solid F322

Example 8 White Solid

TABLE 2 Analytical Data Cmpd. MP IR ¹³C or ¹⁹F No. (° C.) (cm⁻¹) MASS ¹HNMR NMR F1 57-59 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR(CDCl₃) δ 3366, (m/z) 1H), 8.53 (d, J = 8.2 Hz, 1H), 172.22, 168.65,2949, ([M]⁺) 7.99 (d, J = 5.2 Hz, 1H), 159.68, 155.33, 1743, calcd for7.33-7.24 (m, 2H), 7.00-6.91 (m, 148.71, 140.54, 1649, C₂₇H₃₆N₂O₆, 3H),6.87 (d, J = 5.2 Hz, 1H), 130.38, 129.59, 1529, 484.2573; 5.15-5.04 (m,1H), 4.61 (ddd, 121.01, 115.48, 1482, found, J = 10.8, 8.1, 6.9 Hz, 1H),109.49, 81.55, 75.13, 1209 484.2576 4.27-4.18 (m, 1H), 3.93 (s, 3H),56.06, 51.56, 43.20, 2.46-2.33 (m, 1H), 36.39, 33.54, 28.26, 1.93-1.35(m, 7H), 1.32 (d, J = 6.5 Hz, 27.87, 27.51, 23.04, 3H), 1.29-1.05 (m,4H), 22.05, 18.88, 18.41 0.81 (d, J = 6.6 Hz, 3H), 0.80 (d, J = 6.5 Hz,3H) F2 131-133 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.12 (s, ¹³C NMR(CDCl₃) δ 3368, (m/z) 1H), 8.52 (d, J = 8.2 Hz, 1H), 172.25, 168.60,2954, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 155.27, 148.65, 1742, calcd for6.86 (d, J = 5.2 Hz, 1H), 140.48, 130.38, 1650, C₂₅H₄₀N₂O₆, 4.96-4.82(m, 1H), 4.56 (dt, J = 10.5, 109.43, 84.23, 80.42, 1530, 464.2886; 7.4Hz, 1H), 3.93 (s, 3H), 75.68, 56.02, 51.51, 1450, found, 3.46 (dd, J =8.4, 6.3 Hz, 1H), 43.50, 36.53, 33.54, 1265 464.2891 3.27 (dd, J = 8.4,6.5 Hz, 1H), 29.17, 28.08, 28.01, 3.07-2.96 (m, 1H), 27.52, 22.96,22.26, 2.41-2.25 (m, 1H), 1.96-1.31 (m, 19.50, 19.45, 18.80, 7H), 1.43(d, J = 6.4 Hz, 3H), 18.16 1.31-0.95 (m, 5H), 0.95-0.78 (m, 12H) F3118-120 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (s, ¹³C NMR (CDCl₃) δ3366, (m/z) 1H), 8.50 (d, J = 8.1 Hz, 1H), 172.22, 168.61, 2949, ([M]⁺)7.98 (d, J = 5.2 Hz, 1H), 155.30, 148.67, 1743, calcd for 6.87 (d, J =5.2 Hz, 1H), 140.51, 130.40, 1649, C₂₅H₃₈N₂O₆, 4.96-4.84 (m, 1H), 4.55(ddd, J = 10.6, 109.44, 84.29, 78.63, 1583, 462.2730; 8.1, 7.0 Hz, 1H),3.94 (s, 75.66, 56.05, 51.49, 1482, found, 3H), 3.56-3.33 (m, 2H),43.55, 36.42, 33.59, 1209 462.2742 3.10-2.99 (m, 1H), 2.41-2.26 (m,28.06, 27.32, 23.02, 1H), 1.82-1.31 (m, 7H), 22.21, 18.70, 18.11, 1.44(d, J = 6.4 Hz, 3H), 11.12, 3.08, 3.02 1.31-0.93 (m, 5H), 0.90 (d, J =6.6 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H), 0.62-0.51 (m, 2H), 0.27-0.17 (m,2H) F4 101-103 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (d, J = 0.6 Hz,¹³C NMR (CDCl₃) δ 3368, (m/z) 1H), 8.50 (d, J = 8.2 Hz, 172.26, 168.62,2937, ([M]⁺) 1H), 7.99 (d, J = 5.2 Hz, 155.32, 148.70, 1740, calcd for1H), 6.86 (d, J = 5.2 Hz, 1H), 140.51, 130.44, 1649, C₂₄H₃₈N₂O₆,4.97-4.82 (m, 1H), 4.55 (ddd, 109.44, 84.52, 75.68, 1527, 450.2730; J =10.7, 8.2, 7.0 Hz, 1H), 75.44, 56.06, 51.52, 1449, found, 3.94 (s, 3H),3.69-3.59 (m, 1H), 43.49, 36.50, 33.62, 1263 450.2745 3.52-3.41 (m, 1H),28.10, 27.46, 23.54, 3.09-2.97 (m, 1H), 2.40-2.27 (m, 23.03, 22.22,18.77, 1H), 1.83-1.30 (m, 9H), 18.12, 10.71 1.43 (d, J = 6.4 Hz, 3H),1.30-0.95 (m, 4H), 0.94 (t, J = 7.5 Hz, 3H), 0.89 (d, J = 6.7 Hz, 3H),0.88 (d, J = 6.6 Hz, 3H) F5 49-51 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.10(s, ¹³C NMR (CDCl₃) δ 3368, (m/z) 1H), 8.51 (d, J = 8.2 Hz, 1H), 172.20,168.63, 2950, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 155.30, 148.67, 1741,calcd for 6.87 (d, J = 5.2 Hz, 1H), 140.52, 130.35, 1650, C₂₅H₃₇F₃N₂O₆,4.95-4.82 (m, 1H), 4.56 (ddd, J = 10.6, 127.16 (q, J = 276.0 Hz), 1528,518.2604; 8.2, 7.0 Hz, 1H), 3.94 (s, 109.46, 84.75, 75.28, 1450, found,3H), 3.81-3.68 (m, 1H), 71.54, 56.02, 51.49, 1279 518.2602 3.62-3.48 (m,1H), 3.11-2.97 (m, 43.43, 36.44, 33.49, 1H), 2.40-2.28 (m, 1H), 30.77(q, J = 29.0 Hz), 2.28-2.12 (m, 2H), 1.95-1.32 (m, 28.15, 28.05, 27.40,9H), 1.41 (d, J = 6.5 Hz, 3H), 23.04 (q, J = 3.0 Hz), 1.31-0.94 (m, 4H),22.93, 22.14, 18.75, 0.95-0.82 (m, 6H) 18.11 ¹⁹F NMR (CDCl₃) δ −66.41 F6— — ESIMS ¹H NMR (CDCl₃) δ 12.11 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ m/z477.4 1H), 8.52 (d, J = 8.2 Hz, 172.42, 168.60, ([M + H]⁺) 1H), 7.99 (d,J = 5.2 Hz, 155.33, 148.70, 1H), 6.86 (d, J = 5.2 Hz, 1H), 140.52,130.47, 4.94-4.80 (m, 1H), 4.55 (ddd, 109.44 83.57, 82.83, J = 10.9,8.1, 6.6 Hz, 1H), 76.11, 56.07, 51.77, 4.08-3.98 (m, 1H), 3.94 (s, 3H),42.85, 36.86, 33.51, 3.81-3.58 (m, 1H), 3.14 (dd, 32.75, 32.50, 28.27, J= 9.1, 7.8 Hz, 1H), 23.04, 22.97, 22.96, 2.41-2.27 (m, 1H), 1.87-0.99(m, 22.37, 19.15, 18.37 18H), 1.44 (d, J = 6.5 Hz, 3H), 0.89 (d, J = 6.6Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) F7 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ12.11 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ 3369, (m/z) 1H), 8.49 (d, J =8.2 Hz, 172.20, 168.62, 2942, ([M]⁺) 1H), 7.99 (d, J = 5.2 Hz, 155.33,148.70, 1742, calcd for 1H), 6.87 (d, J = 5.2 Hz, 1H), 140.51, 130.43,1650, C₂₂H₃₄N₂O₆, 4.95-4.80 (m, 1H), 4.56 (ddd, 109.45, 86.37, 75.42,1530, 422.2417; J = 10.7, 8.2, 7.1 Hz, 1H), 61.23, 56.07, 51.49, 1482,found, 3.94 (s, 3H), 3.51 (s, 3H), 43.53, 36.48, 33.62, 1265 422.24273.03-2.88 (m, 1H), 2.41-2.26 (m, 28.24, 28.17, 27.21, 1H), 1.85-1.31 (m,7H), 23.09, 22.17, 18.71, 1.44 (d, J = 6.4 Hz, 3H), 18.07 1.31-0.93 (m,4H), 0.90 (d, J = 6.6 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H) F8 — (Neat)HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ 3369,(m/z) 1H), 8.47 (d, J = 8.1 Hz, 176.20, 172.28, 2952, ([M]⁺) 1H), 7.99(d, J = 5.2 Hz, 168.63, 155.36, 1734, calcd for 1H), 6.87 (d, J = 5.2Hz, 1H), 148.75, 140.50, 1651, C₂₇H₄₀N₂O₇, 5.08-4.96 (m, 1H), 130.41,109.47, 76.04, 1529, 504.2836; 4.94-4.83 (m, 1H), 4.59 (ddd, J = 10.8,73.69, 56.08, 51.49, 1482, found, 8.1, 7.1 Hz, 1H), 3.94 (s, 44.10,41.92, 36.35, 1265, 504.2861 3H), 2.81-2.67 (m, 1H), 33.46, 30.08,30.00, 1176 2.44-2.31 (m, 1H), 2.01-1.33 (m, 28.00, 27.90, 27.40, 14H),1.33-1.14 (m, 3H), 25.71, 25.70, 22.90, 1.27 (d, J = 6.3 Hz, 3H), 22.20,18.68, 17.56 1.14-0.96 (m, 2H), 0.86 (d, J = 6.6 Hz, 3H), 0.85 (d, J =6.6 Hz, 3H) F9 — — ESIMS ¹H NMR (CDCl₃) δ 12.11 (d, J = 0.6 Hz, ¹³C NMR(CDCl₃) δ m/z 489.3 1H), 8.49 (d, J = 8.2 Hz, 172.21, 168.62, ([M + H]⁺)1H), 7.99 (d, J = 5.2 Hz, 155.31, 148.69, 1H), 6.87 (d, J = 5.2 Hz, 1H),140.51, 130.42, 4.97-4.84 (m, 1H), 4.55 (ddd, 109.44, 84.33, 78.51, J =10.7, 8.2, 7.0 Hz, 1H), 75.66, 56.05, 51.49, 3.94 (s, 3H), 3.49 (dd, J =9.6, 7.0 Hz, 40.09, 38.30, 35.05, 1H), 3.37 (dd, J = 9.6, 6.8 Hz, 34.59,33.63, 32.34, 1H), 3.07-2.95 (m, 1H), 27.44, 26.68, 26.48, 2.40-2.28 (m,1H), 26.15, 18.77, 18.10, 1.80-1.44 (m, 11H), 1.43 (d, J = 6.4 Hz,11.14, 3.16, 2.94 3H), 1.42-0.68 (m, 9H), 0.61-0.50 (m, 2H), 0.28-0.17(m, 2H) F10 69-71 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (d, J = 0.6 Hz,¹³C NMR (CDCl₃) δ 3367, (m/z) 1H), 8.45 (d, J = 8.2 Hz, 172.09, 168.64,2939, ([M]⁺) 1H), 7.98 (d, J = 5.2 Hz, 161.31 (d, J = 243.7 Hz), 1740,calcd for 1H), 7.17-7.08 (m, 2H), 155.33, 148.70, 1648, C₂₇H₃₃FN₂O₆,7.02-6.93 (m, 2H), 6.86 (d, J = 5.2 Hz, 140.53, 136.24 (d, J = 3.2 Hz),1528, 500.2323; 1H), 5.00-4.86 (m, 1H), 130.37, 1447, found, 4.56 (ddd,J = 10.9, 8.2, 7.0 Hz, 130.14 (d, J = 7.7 Hz), 1214, 500.2329 1H), 3.93(s, 3H), 115.16 (d, J = 21.1 Hz), 1056 3.58 (dd, J = 9.7, 7.0 Hz, 1H),109.47, 83.69, 3.45 (dd, J = 9.7, 6.8 Hz, 1H), 78.79, 75.46, 56.06,3.21-3.14 (m, 1H), 3.14-3.07 (m, 51.41, 46.09, 36.06, 1H), 2.38-2.23 (m,2H), 33.55, 26.61, 18.73, 1.91-1.77 (m, 1H), 1.64-1.51 (m, 18.10, 11.17,3.16, 2H), 1.48-1.37 (m, 1H), 3.02 1.47 (d, J = 6.4 Hz, 3H), ¹⁹F NMR(CDCl₃) δ −117.38 1.32-1.20 (m, 1H), 1.18-1.06 (m, 1H), 0.96-0.82 (m,1H), 0.65-0.53 (m, 2H), 0.31-0.19 (m, 2H) F11 88-90 (Neat) HRMS-ESI ¹HNMR (CDCl₃) δ 12.07 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ 3370, (m/z) 1H),8.48 (d, J = 8.2 Hz, 172.11, 168.68, 2939, ([M]⁺) 1H), 7.98 (d, J = 5.2Hz, 161.33 (d, J = 243.7 Hz), 1745, calcd for 1H), 7.37-7.27 (m, 2H),159.53, 155.36, 1650, C₂₉H₃₁FN₂O₆, 7.12-6.90 (m, 7H), 6.86 (d, J = 5.2Hz, 148.74, 140.56, 1509, 522.2166; 1H), 5.21-5.07 (m, 1H), 135.77, (d,J = 3.2 Hz), 1327, found, 4.62 (ddd, J = 11.0, 8.2, 6.9 Hz, 130.34,130.11 (d, J = 7.8 Hz), 1210 522.2182 1H), 3.93 (s, 3H), 129.75, 2.98(dd, J = 13.5, 3.4 Hz, 1H), 121.32, 115.47, 2.44-2.27 (m, 2H), 115.16(d, J = 21.1 Hz), 2.14-1.99 (m, 1H), 1.76-1.48 (m, 109.52, 80.93, 74.89,3H), 1.38-1.21 (m, 2H), 56.08, 51.50, 45.70, 1.36 (d, J = 6.5 Hz, 3H),36.12, 33.50, 26.77, 1.11-0.97 (m, 1H) 18.89, 18.38 ¹⁹F NMR (CDCl₃) δ−117.22 F12 65-67 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR(CDCl₃) δ 3366, (m/z) 1H), 8.46 (d, J = 8.2 Hz, 1H), 172.10, 168.65,2938, ([M]⁺) 7.97 (d, J = 5.2 Hz, 1H), 161.29 (d, J = 243.7 Hz), 1742,calcd for 7.17-7.06 (m, 2H), 7.02-6.92 (m, 155.32, 148.70, 1649,C₂₆H₃₁FN₂O₆, 2H), 6.86 (d, J = 5.2 Hz, 1H), 140.54, 136.20 (d, J = 3.2Hz), 1529, 486.2166; 6.03-5.87 (m, 1H), 5.34 (dq, 134.28, 1218 found, J= 17.2, 1.6 Hz, 1H), 130.34, 130.13 (d, J = 7.7 Hz), 486.2172 5.21 (dq,J = 10.4, 1.3 Hz, 1H), 117.12, 5.00-4.88 (m, 1H), 4.57 (ddd, 115.14 (d,J = 21.1 Hz), J = 10.9, 8.2, 7.0 Hz, 1H), 109.50, 84.06, 4.29 (ddt, J =12.2, 5.5, 1.5 Hz, 75.29, 74.68, 56.05, 1H), 4.11 (ddt, J = 12.3, 5.6,51.42, 45.92, 36.08, 1.4 Hz, 1H), 3.93 (s, 3H), 33.49, 26.58, 18.75,3.30-3.18 (m, 1H), 3.13-3.01 (m, 18.14 1H), 2.41-2.23 (m, 2H), ¹⁹F NMR(CDCl₃) δ −117.33 1.91-1.75 (m, 1H), 1.68-1.53 (m, 2H), 1.50-1.37 (m,1H), 1.48 (d, J = 6.4 Hz, 3H), 1.37-1.17 (m, 1H), 0.98-0.81 (m, 1H) F13127-129 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (d, J = 0.6 Hz, ¹³C NMR(CDCl₃) δ 3367, (m/z) 1H), 8.45 (d, J = 8.2 Hz, 172.12, 168.64, 2937,([M]⁺) 1H), 7.98 (d, J = 5.2 Hz, 161.30 (d, J = 243.7 Hz), 1741, calcdfor 1H), 7.17-7.05 (m, 2H), 155.34, 148.71, 1649, C₂₆H₃₃FN₂O₆, 7.02-6.92(m, 2H), 6.86 (d, J = 5.2 Hz, 140.53, 136.31 (d, J = 3.3 Hz), 1528,488.2323; 1H), 4.99-4.86 (m, 1H), 130.39, 1508, found, 4.56 (ddd, J =10.9, 8.2, 7.0 Hz, 130.13 (d, J = 7.7 Hz), 1217 488.2322 1H), 3.94 (s,3H), 115.15 (d, J = 21.1 Hz), 3.81-3.66 (m, 1H), 3.52 (dt, J = 8.7,109.47, 83.89, 6.7 Hz, 1H), 3.21-3.12 (m, 75.66, 75.48, 56.07, 1H),3.11-3.01 (m, 1H), 51.43, 46.10, 36.01, 2.39-2.23 (m, 2H), 1.87-1.73 (m,33.56, 26.61, 23.59, 1H), 1.71-1.52 (m, 4H), 18.77, 18.10, 10.74 1.47(d, J = 6.5 Hz, 3H), ¹⁹F NMR (CDCl₃) δ- 1.46-1.36 (m, 1H), 1.33-1.18 (m,117.43 1H), 0.98 (t, J = 7.4 Hz, 3H), 0.95-0.83 (m, 1H) F14 71-73 (Neat)HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (s, ¹³C NMR (CDCl₃) δ 3368, (m/z) 1H),8.45 (d, J = 8.2 Hz, 1H), 172.12, 168.63, 2939, ([M]⁺) 7.98 (d, J = 5.2Hz, 1H), 161.30 (d, J = 243.6 Hz), 1741, calcd for 7.17-7.04 (m, 2H),7.02-6.91 (m, 155.34, 148.71, 1650, C₂₇H₃₅FN₂O₆, 2H), 6.86 (d, J = 5.2Hz, 1H), 140.52, 136.35 (d, J = 3.2 Hz), 1529, 502.2479; 5.00-4.84 (m,1H), 4.56 (ddd, 130.39, 1508, found, J = 11.0, 8.2, 7.0 Hz, 1H), 130.12(d, J = 7.6 Hz), 1219 502.2485 3.94 (s, 3H), 3.56 (dd, J = 8.4, 6.3 Hz,115.15 (d, J = 21.1 Hz), 1H), 3.34 (dd, J = 8.4, 6.5 Hz, 109.47, 83.62,1H), 3.18-3.11 (m, 1H), 80.71, 75.51, 56.07, 3.11-3.01 (m, 1H), 51.44,46.22, 35.92, 2.40-2.24 (m, 2H), 1.97-1.73 (m, 33.57, 29.27, 26.58, 2H),1.68-1.52 (m, 2H), 19.52, 19.49, 18.80, 1.49-1.36 (m, 1H), 1.47 (d, J =6.5 Hz, 18.17 3H), 1.33-1.19 (m, 1H), ¹⁹F NMR (CDCl₃) δ −117.44 0.97 (d,J = 6.7 Hz, 3H), 0.96 (d, J = 6.7 Hz, 3H), 0.93-0.83 (m, 1H) F15 164-166(Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.12 (s, ¹³C NMR (CDCl₃) δ 3369, (m/z)1H), 8.47 (d, J = 8.2 Hz, 1H), 171.96, 168.62, 2941, ([M]⁺) 7.96 (d, J =5.2 Hz, 1H), 161.25 (d, J = 243.8 Hz), 1743, calcd for 7.19-7.05 (m,2H), 7.03-6.91 (m, 155.26, 148.63, 1649, C₂₅H₂₉F₃N₂O₆, 2H), 6.86 (d, J =5.2 Hz, 1H), 140.53, 135.81 (d, J = 3.2 Hz), 1529, 510.1978; 5.88 (tt, J= 55.1, 3.9 Hz, 1H), 130.19, 1509, found, 4.93 (dq, J = 9.4, 6.2 Hz,1H), 130.09 (d, J = 7.7 Hz), 1217 510.1977 4.65-4.53 (m, 1H), 115.10 (d,J = 21.0 Hz), 4.07-3.91 (m, 1H), 3.91 (s, 3H), 113.87 (t, J = 241.0 Hz),3.86-3.71 (m, 1H), 109.51, 3.31-3.19 (m, 1H), 3.09-2.98 (m, 85.27,74.63, 72.49 (t, 1H), 2.42-2.22 (m, 2H), J = 27.5 Hz), 55.95, 1.90-1.76(m, 1H), 1.71-1.48 (m, 51.29, 45.75, 35.77, 2H), 1.47 (d, J = 6.5 Hz,3H), 33.32, 26.38, 18.65, 1.47-1.36 (m, 1H), 18.00 1.35-1.20 (m, 1H),0.95-0.80 (m, ¹⁹F NMR (CDCl₃) δ −117.13, 1H) −125.48 (d, J = 9.4 Hz, 2F)F16 70-72 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.05 (s, ¹³C NMR (CDCl₃) δ3368, (m/z) 1H), 8.43 (d, J = 8.1 Hz, 1H), 176.13, 172.14, 2946, ([M]⁺)7.98 (d, J = 5.2 Hz, 1H), 168.65, 161.39 (d, J = 244.1 Hz), 1732, calcdfor 7.11-7.02 (m, 2H), 7.01-6.92 (m, 155.36, 1649, C₂₉H₃₅FN₂O₇, 2H),6.86 (d, J = 5.2 Hz, 1H), 148.75, 140.52, 1529, 542.2428; 5.13-4.92 (m,2H), 4.60 (ddd, 135.50 (d, J = 3.2 Hz), 1509, found, J = 11.0, 8.1, 7.0Hz, 1H), 130.34, 130.06 (d, J = 7.8 Hz), 1448, 542.2417 3.94 (s, 3H),2.82-2.57 (m, 2H), 115.26 (d, J = 21.1 Hz), 1263 2.44-2.25 (m, 2H),109.49, 2.04-1.43 (m, 11H), 1.38-1.18 (m, 75.44, 73.45, 56.08, 2H), 1.30(d, J = 5.8 Hz, 3H), 51.40, 44.11, 44.01, 1.05-0.93 (m, 1H) 35.92,33.37, 30.07, 30.05, 26.79, 25.73, 25.71, 18.66, 17.55 ¹⁹F NMR (CDCl₃) δ−117.01 F17 177-179 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 12.05 (s, ¹³C NMR(CDCl₃) δ 3370, (m/z) 1H), 8.44 (d, J = 8.1 Hz, 1H), 176.46, 172.13,2939, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 168.65, 161.39 (d, J = 244.2 Hz),1735, calcd for 7.12-7.02 (m, 2H), 7.02-6.91 (m, 155.36, 1650,C₂₇H₃₃FN₂O₇, 2H), 6.86 (d, J = 5.2 Hz, 1H), 148.74, 140.52, 1529,516.2272; 5.13-4.96 (m, 2H), 4.61 (ddd, 135.46 (d, J = 3.2 Hz), 1509,found, J = 11.0, 8.1, 7.0 Hz, 1H), 130.33, 130.05 (d, J = 7.8 Hz), 1264516.2257 3.94 (s, 3H), 2.70-2.62 (m, 1H), 115.27 (d, J = 21.1 Hz), 2.59(hept, J = 7.0 Hz, 1H), 109.50, 2.43-2.28 (m, 2H), 75.38, 73.38, 56.07,2.01-1.86 (m, 1H), 1.77-1.46 (m, 51.39, 44.09, 35.84, 3H), 1.35-1.20 (m,1H), 34.22, 33.36, 26.71, 1.30 (d, J = 5.9 Hz, 3H), 1.22 (d, J = 7.0 Hz,19.09, 19.00, 18.65, 3H), 1.22 (d, J = 7.0 Hz, 17.51 3H), 1.06-0.93 (m,1H) ¹⁹F NMR (CDCl₃) δ −116.98 F18 — — ESIMS ¹H NMR (CDCl₃) δ 12.11 (s,¹³C NMR (CDCl₃) δ m/z 485.4 1H), 8.46 (d, J = 8.2 Hz, 1H), 172.16,168.65, ([M + H]⁺) 7.96 (d, J = 5.2 Hz, 1H), 155.33, 148.71, 7.28 (dd, J= 10.2, 4.4 Hz, 2H), 140.78, 140.54, 7.23-7.12 (m, 3H), 6.85 (d, J = 5.2Hz, 130.39, 128.86, 1H), 4.99-4.86 (m, 128.38, 125.93, 1H), 4.55 (tt, J= 25.8, 12.9 Hz, 109.48, 83.66, 80.66, 1H), 3.92 (s, 3H), 75.54, 56.06,51.45, 3.56 (dd, J = 8.3, 6.3 Hz, 1H), 46.14, 36.73, 33.58, 3.34 (dd, J= 8.3, 6.6 Hz, 1H), 29.27, 26.55, 19.55, 3.19-3.08 (m, 2H), 2.42-2.22(m, 19.50, 18.79, 18.19 2H), 1.97-1.78 (m, 2H), 1.69-1.52 (m, 2H),1.51-1.41 (m, 5H), 0.96 (dt, J = 13.2, 6.6 Hz, 6H), 0.82-09.82 (m, 1H)F19 — — ESIMS ¹H NMR (CDCl₃) δ 12.12 (s, ¹³C NMR (75 MHz, m/z 483.5 1H),8.47 (d, J = 8.2 Hz, 1H), CDCl₃) δ 172.01, ([M + H]⁺) 7.94 (d, J = 5.2Hz, 1H), 168.54, 155.18, 7.35-7.23 (m, 2H), 7.18 (td, J = 6.4, 148.58,140.54, 1.5 Hz, 3H), 6.84 (d, J = 5.3 Hz, 140.42, 130.22, 1H), 4.94 (dq,J = 9.1, 128.75, 128.26, 6.4 Hz, 1H), 4.57 (ddd, J = 10.9, 125.83,109.42, 83.61, 8.2, 7.0 Hz, 1H), 3.90 (s, 78.59, 75.37, 55.93, 3H), 3.58(dd, J = 9.7, 7.0 Hz, 51.34, 45.94, 36.79, 1H), 3.44 (dd, J = 9.7, 6.8Hz, 33.42, 26.52, 18.65, 1H), 3.31-3.03 (m, 2H), 18.02, 11.11, 3.08,2.41-2.19 (m, 2H), 1.88 (tt, J = 8.3, 2.94 4.0 Hz, 1H), 1.58 (ddt, J =12.9, 6.9, 2.6 Hz, 2H), 1.47 (d, J = 6.4 Hz, 3H), 1.53-1.38 (m,overlapping, 1H), 1.30-1.20 (m, 1H), 1.17-1.02 (m, 1H), 0.99-0.78 (m,1H), 0.69-0.48 (m, 2H), 0.25 (qd, J = 4.2, 1.7 Hz, 2H) F20 — — ESIMS ¹HNMR (CDCl₃) δ 12.08 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ m/z 505.4 1H),8.47 (d, J = 8.1 Hz, 172.24, 168.77, ([M + H]⁺) 1H), 7.98 (d, J = 5.2Hz, 159.73, 155.46, 1H), 7.40-7.21 (m, 3H), 148.84, 140.65, 7.21-7.08(m, 3H), 7.08-6.93 (m, 140.27, 130.46, 3H), 6.89-6.82 (m, 1H), 129.83,128.91, 5.20-5.07 (m, 1H), 4.62 (ddd, J = 11.0, 128.47, 126.13, 8.2, 7.0Hz, 1H), 4.36 (t, 121.38, 115.65, J = 8.9 Hz, 1H), 3.93 (s, 3H), 109.61,81.17, 75.05, 3.78-3.62 (m, 1H), 3.03 (dd, 56.18, 51.61, 45.75, J =13.3, 3.3 Hz, 1H), 37.00, 33.64, 26.80, 2.35 (ddd, J = 11.3, 9.4, 6.5Hz, 18.98, 18.51 2H), 2.20-2.07 (m, 1H), 1.78-1.64 (m, 2H), 1.64-1.50(m, 1H), 1.36 (d, J = 6.5 Hz, 3H), 1.34-1.27 (m, 1H), 1.08-0.97 (m, 1H)F21 — — ESIMS ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR (CDCl₃) δ m/z 471.41H), 8.45 (d, J = 8.2 Hz, 1H), 172.26, 168.73, ([M + H]⁺) 7.97 (d, J =5.2 Hz, 1H), 155.43, 148.81, 7.33-7.24 (m, 2H), 7.23-7.13 (m, 140.83,140.63, 3H), 6.85 (d, J = 5.2 Hz, 1H), 130.50, 128.96, 4.93 (dq, J =9.2, 6.4 Hz, 1H), 128.47, 126.03, 4.56 (ddd, J = 11.0, 8.2, 7.0 Hz,109.57, 84.05, 75.72, 1H), 3.93 (s, 3H), 75.62, 56.17, 51.55, 3.79-3.67(m, 1H), 3.53 (dt, J = 8.7, 46.11, 36.93, 33.70, 6.7 Hz, 1H), 3.18 (t, J= 9.0 Hz, 26.69, 23.70, 18.87, 1H), 3.15-3.06 (m, 1H), 18.23, 10.862.41-2.23 (m, 2H), 1.86 (ddd, J = 12.1, 8.4, 3.9 Hz, 1H), 1.72-1.55 (m,4H), 1.48 (d, J = 6.4 Hz, 3H), 1.45-1.38 (m, 1H), 1.33-1.19 (m, 1H),0.98 (t, J = 7.4 Hz, 3H), 0.94-0.82 (m, 1H) F22 — — ESIMS ¹H NMR (CDCl₃)δ 12.10 (s, ¹³C NMR (CDCl₃) δ m/z 497.4 1H), 8.45 (d, J = 8.2 Hz, 1H),172.34, 168.60, ([M + H]⁺) 7.97 (d, J = 5.2 Hz, 1H), 155.32, 148.70,7.38-7.23 (m, 2H), 7.22-7.13 (m, 141.05, 140.51, 3H), 6.85 (d, J = 5.2Hz, 1H), 130.40, 128.87, 4.91 (dq, J = 9.1, 6.5 Hz, 1H), 128.37, 125.87,4.54 (ddd, J = 11.1, 8.2, 6.6 Hz, 109.45, 83.87, 82.31, 1H), 4.18-4.06(m, 1H), 75.95, 56.06, 51.68, 3.93 (s, 3H), 3.30 (t, J = 8.6 Hz, 45.22,36.93, 33.42, 1H), 3.20 (dd, J = 13.3, 32.84, 32.57, 27.89, 3.3 Hz, 1H),2.40-2.16 (m, 23.05, 22.99, 19.10, 2H), 1.87-1.67 (m, 7H), 18.391.66-1.52 (m, 4H), 1.49 (d, J = 6.5 Hz, 3H), 1.46-1.36 (m, 1H),1.32-1.14 (m, 1H), 1.04-0.84 (m, 1H) F23 — — ESIMS ¹H NMR (CDCl₃) δ12.09 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ m/z 457.2 1H), 8.45 (d, J = 8.2Hz, 172.15, 168.63, ([M + H]⁺) 1H), 7.98 (d, J = 5.2 Hz, 155.33, 148.71,1H), 7.33-7.24 (m, 2H), 140.68, 140.52, 7.23-7.15 (m, 3H), 6.85 (d, J =5.1 Hz, 130.40, 128.86, 1H), 4.93 (dq, J = 9.2, 6.4 Hz, 128.37, 125.94,1H), 4.56 (ddd, J = 10.9, 109.46, 84.17, 75.48, 8.2, 7.0 Hz, 1H), 3.93(s, 3H), 69.26, 56.07, 51.45, 3.83 (dq, J = 8.8, 6.9 Hz, 1H), 45.88,36.92, 33.61, 3.64 (dq, J = 8.9, 7.0 Hz, 1H), 26.62, 18.74, 18.05,3.24-3.15 (m, 1H), 3.11 (dd, 15.73 J = 13.3, 3.4 Hz, 1H), 2.44-2.20 (m,2H), 1.85 1.90-1.79 (m, 1H), 1.68-1.53 (m, 2H), 1.52-1.41 (m, 1H), 1.48(d, J = 6.5 Hz, 3H), 1.31-1.21 (m, 1H), 1.25 (t, J = 6.9 Hz, 3H),0.95-0.83 (m, 1H) F24 — — ESIMS ¹H NMR (CDCl₃) δ 12.09 (d, J = 0.6 Hz,¹³C NMR (75 MHz, m/z 487.4 1H), 8.45 (d, J = 8.2 Hz, CDCl₃) δ 172.28,([M + H]⁺) 1H), 7.97 (d, J = 5.2 Hz, 168.83, 155.52, 1H), 7.33-7.23 (m,2H), 148.91, 140.89, 7.23-7.15 (m, 3H), 6.85 (dd, J = 5.3, 140.72,130.59, 0.6 Hz, 1H), 4.96 (dq, J = 9.2, 129.09, 128.99, 6.4 Hz, 1H),4.56 (ddd, J = 10.9, 128.55, 126.12, 8.2, 7.0 Hz, 1H), 109.68, 84.89,75.53, 3.98-3.94 (m, 1H), 3.93 (s, 3H), 73.05, 72.36, 59.29, 3.73 (ddd,J = 10.4, 5.7, 3.5 Hz, 56.27, 51.64, 45.98, 1H), 3.62-3.53 (m, 2H),37.00, 33.80, 26.79, 3.40 (s, 3H), 3.24 (t, J = 9.1 Hz, 18.99, 18.381H), 3.17 (dd, J = 13.2, 3.4 Hz, 1H), 2.43-2.24 (m, 2H), 1.98-1.85 (m,1H), 1.60 (dtt, J = 9.1, 6.6, 3.2 Hz, 2H), 1.54-1.42 (m, 4H), 1.33-1.20(m, 1H), 0.95-0.81 (m, 1H) F25 — — ESIMS ¹H NMR (CDCl₃) δ 12.11 (d, J =0.6 Hz, ¹³C NMR (CDCl₃) δ m/z 491.3 1H), 8.49 (d, J = 8.2 Hz, 172.25,168.61, ([M + H]⁺) 1H), 7.99 (d, J = 5.2 Hz, 155.33, 148.70, 1H), 6.86(d, J = 5.2 Hz, 1H), 140.50, 130.45, 4.89 (dq, J = 9.2, 6.4 Hz, 1H),109.44, 84.26, 80.38, 4.55 (ddd, J = 10.8, 8.2, 7.0 Hz, 75.75, 56.06,51.53, 1H), 3.94 (s, 3H), 40.00, 38.14, 35.09, 3.46 (dd, J = 8.4, 6.1Hz, 1H), 34.60, 33.65, 32.27, 3.24 (dd, J = 8.4, 6.6 Hz, 1H), 29.21,27.42, 26.69, 2.98 (t, J = 8.8 Hz, 1H), 2.34 (dt, J = 13.2, 26.52,26.20, 19.58, 6.7 Hz, 1H), 19.47, 18.81, 18.17 1.83 (hept, J = 6.5 Hz,1H), 1.77-1.61 (m, 8H), 1.42 (d, J = 6.4 Hz, 3H), 1.40-1.08 (m, 8H),1.02-0.93 (m, 8H), 0.76 (qd, J = 13.6, 12.2, 4.1 Hz, 1H) F26 — (ThinHRMS-ESI ¹H NMR (CDCl₃) δ 12.07 (s, — Film) (m/z) 1H), 8.47 (d, J = 8.1Hz, 1H), 3366, ([M]⁺) 7.99 (d, J = 5.1 Hz, 1H), 2938, calcd for 7.31(dd, J = 8.7, 7.3 Hz, 2H), 1743, C₃₀H₃₄N₂O₇, 7.09-6.94 (m, 5H), 6.87 (d,J = 5.3 Hz, 1649, 534.2366; 1H), 6.80 (d, J = 8.7 Hz, 1530, found, 2H),5.14 (dq, J = 9.3, 6.4 Hz, 1512, 534.2373 1H), 4.70-4.53 (m, 1H), 12434.34 (t, J = 8.9 Hz, 1H), 3.94 (s, 3H), 3.78 (s, 3H), 2.96 (dd, J =13.8, 3.2 Hz, 1H), 2.33 (ddd, J = 17.7, 12.3, 9.0 Hz, 2H), 2.05 (s, 2H),1.69 (dt, J = 10.7, 5.0 Hz, 2H), 1.38-1.25 (m, 1H), 1.36 (d, J = 6.5 Hz,3H), 1.14-0.88 (m, 1H) F27 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (s, ¹³CNMR (CDCl₃) δ (m/z) 1H), 8.55 (d, J = 8.2 Hz, 1H), 172.21, 168.64,([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 159.73, 155.35, calcd for 7.35-7.23 (m,2H), 6.95 (d, J = 7.5 Hz, 148.72, 140.53, C₂₈H₃₆N₂O₆, 3H), 6.86 (d, J =5.2 Hz, 130.40, 129.59, 496.2573; 1H), 5.10 (dq, J = 9.1, 6.5 Hz,120.98, 115.55, found, 1H), 4.61 (ddd, J = 10.8, 8.1, 109.47, 81.58,75.16, 496.2600 7.0 Hz, 1H), 4.20 (t, J = 8.7 Hz, 56.08, 51.58, 42.02,1H), 3.92 (s, 3H), 37.25, 36.82, 33.66, 2.45-2.31 (m, 1H), 1.97-1.35 (m,33.63, 31.76, 25.04, 14H), 1.31 (d, J = 6.5 Hz, 3H), 19.03, 18.401.22-1.06 (m, 1H), 1.10-0.89 (m, 2H) F28 — (Thin HRMS-ESI ¹H NMR (CDCl₃)δ 12.06 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.43 (d, J =8.1 Hz, 176.16, 172.19, 2941, ([M]⁺) 1H), 7.98 (d, J = 5.2 Hz, 168.64,157.98, 1731, calcd for 1H), 7.07-6.99 (m, 2H), 155.37, 148.76, 1512C₃₀H₃₈N₂O₈, 6.89-6.77 (m, 3H), 5.12-4.97 (m, 140.50, 131.86, 554.2628;2H), 4.60 (ddd, J = 11.0, 8.1, 130.38, 129.64, found, 7.0 Hz, 1H), 3.94(s, 3H), 113.87, 109.48, 75.53, 554.2634 3.79 (s, 3H), 2.82-2.71 (m,1H), 73.53, 56.08, 55.24, 2.64 (dd, J = 13.6, 3.8 Hz, 51.43, 44.17,44.04, 1H), 2.38-2.27 (m, 2H), 35.75, 33.45, 30.10, 2.02-1.56 (m, 13H),1.30 (d, J = 5.8 Hz, 30.03, 26.72, 25.73, 3H), 1.02-0.92 (m, 18.66,17.57 1H) F29 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (d, J = 0.6 Hz,¹⁹F NMR (CDCl₃) δ −89.56 Film) (m/z) 1H), 8.45 (d, J = 8.2 Hz, 2938,([M]⁺) 1H), 7.97 (d, J = 5.2 Hz, 1741, calcd for 1H), 7.12-7.03 (m, 4H),1649, C₂₈H₃₆F₂N₂O₇, 6.86 (d, J = 5.1 Hz, 1H), 6.83 (d, J = 2.0 Hz, 1528,550.2491; 3H), 4.92 (dq, J = 9.2, 1448, found, 6.4 Hz, 1H), 4.56 (ddd, J= 10.9, 1264 550.2503 8.2, 7.0 Hz, 1H), 3.93 (s, 3H), 3.79 (s, 3H), 3.18(t, J = 9.0 Hz, 1H), 3.00 (dd, J = 13.4, 3.5 Hz, 1H), 2.39-2.11 (m, 4H),1.87-1.74 (m, 1H), 1.67 (t, J = 18.7 Hz, 3H), 1.62-1.49 (m, 1H), 1.45(s, 3H), 1.38-1.17 (m, 2H), 0.96-0.82 (m, 1H) F30 — (Thin HRMS-ESI ¹HNMR (CDCl₃) δ 12.09 (d, J = 0.9 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H),8.44 (d, J = 8.2 Hz, 172.13, 168.62, 3366, ([M]⁺) 1H), 7.98 (dd, J =5.2, 1.1 Hz, 157.86, 155.33, 2938, calcd for 1H), 7.09 (d, J = 8.4 Hz,148.71, 140.51, 1741, C₂₈H₃₆N₂O₇, 1H), 6.92-6.74 (m, 2H), 132.60,129.73, 1649, 512.2523; 5.03-4.85 (m, 1H), 4.56 (dt, J = 10.7, 113.80,109.45, 99.99, 1528, found, 7.6 Hz, 1H), 3.94 (s, 3H), 83.78, 78.76,75.52, 1511, 512.2536 3.79 (s, 3H), 3.58 (dd, J = 9.7, 56.07, 55.24,51.44, 1243 7.0 Hz, 1H), 3.45 (dd, J = 9.7 46.11, 35.94, 33.63, 6.8 Hz,1H), 3.17 (t, J = 9.0 Hz, 26.56, 18.73, 18.12, 1H), 3.09 (d, J = 13.6Hz, 11.18, 3.16, 3.02 1H), 2.34-2.20 (m, 2H), 1.90-1.78 (m, 1H),1.60-1.51 (m, 5H), 1.47 (d, J = 6.4 Hz, 3H), 1.35-1.18 (m, 1H),1.18-1.07 (m, 1H), 0.93-0.82 (m, 1H), 0.70-0.40 (m, 2H), 0.34-0.22 (m,2H) F31 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR (CDCl₃) δFilm) (m/z) 1H), 8.49 (d, J = 8.2 Hz, 1H), 172.23, 168.62, 3367, ([M]⁺)7.99 (d, J = 5.2 Hz, 1H), 155.34, 148.71, 2942, calcd for 6.86 (d, J =5.2 Hz, 1H), 4.91 (dq, J = 9.3, 140.52, 130.46, 2868, C₂₆H₃₈N₂O₆, 6.4Hz, 1H), 4.55 (ddd, 109.45, 84.31, 78.54, 1740, 474.2730; J = 10.7, 8.2,6.9 Hz, 1H), 75.64, 56.07, 51.54, 1649, found, 3.94 (s, 3H), 3.50 (dd J= 9.6, 7.0 Hz, 42.29, 37.27, 36.90, 1528, 474.2743 1H), 3.36 (dd, J =9.6, 6.8 Hz, 33.97, 33.67, 31.85, 1057 1H), 3.01 (t, J = 8.9 Hz, 27.52,25.11, 25.08, 1H), 2.34 (dt, J = 13.3, 6.8 Hz, 18.93, 18.11, 11.14, 1H),1.92-1.45 (m, 13H), 3.14, 2.95 1.43 (d, J = 6.4 Hz, 3H), 1.40-1.29 (m,1H), 1.16-0.94 (m, 4H), 0.59-0.49 (m, 2H), 0.21 (dt, J = 6.0, 4.5 Hz,2H) F32 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR (CDCl₃) δFilm) (m/z) 1H), 8.45 (d, J = 8.2 Hz, 1H), 172.15, 168.61, 3368, ([M]⁺)7.98 (d, J = 5.2 Hz, 1H), 157.83, 155.32, 2939, calcd for 7.08 (d, J =8.6 Hz, 2H), 6.86 (d, J = 5.3 Hz, 148.69, 140.51, 1742, C₂₈H₃₈N₂O₇, 1H),6.83 (d, J = 8.6 Hz, 132.72, 130.39, 1650, 514.2679; 2H), 4.93 (dq, J =9.3, 6.4 Hz, 129.70, 113.77, 1529, found, 1H), 4.56 (ddd, J = 10.9,109.44, 83.66, 80.65, 1511, 514.2659 8.2, 7.0 Hz, 1H), 3.93 (s, 3H),75.56, 56.06, 55.23, 1244 3.79 (s, 3H), 3.56 (dd, J = 8.4, 51.44, 46.25,35.76, 6.2 Hz, 1H), 3.34 (dd, J = 8.4, 33.62, 29.26, 26.50, 6.5 Hz, 1H),3.15 (t, J = 9.0 Hz, 19.54, 19.49, 18.77, 1H), 3.05 (dd, J = 13.3, 18.183.2 Hz, 1H), 2.37-2.22 (m, 2H), 1.91 (dq, J = 13.2, 6.6 Hz, 1H), 1.80(ddq, J = 12.0, 7.5, 4.3, 3.6 Hz, 1H), 1.66-1.54 (m, 3H), 1.53-1.38 (m,1H), 1.46 (d, J = 6.4 Hz, 3H), 0.97 (dd, J = 6.7, 4.8 Hz, 6H), 0.94-0.81(m, 1H) F33 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃)δ Film) (m/z) 1H), 8.45 (d, J = 8.2 Hz, 1H), 172.15, 168.61, 3369,([M]⁺) 7.98 (d, J = 5.1 Hz, 1H), 157.83, 155.32, 2938, calcd for 7.08(d, J = 8.6 Hz, 2H), 6.86 (d, J = 5.3 Hz, 148.70, 140.51, 2877,C₂₇H₃₆N₂O₇, 1H), 6.83 (d, J = 8.6 Hz, 132.67, 130.40, 1742, 500.2523;2H), 4.93 (dq, J = 9.2, 6.4 Hz, 129.71, 113.77, 1650, found, 1H), 4.56(ddd, J = 11.0, 109.44, 83.95, 75.62, 1529, 500.2522 8.3, 7.0 Hz, 1H),3.94 (s, 3H), 75.53, 56.07, 55.23, 1512, 3.79 (s, 3H), 3.73 (dt, J =8.6, 51.45, 46.12, 35.86, 1244 6.5 Hz, 1H), 3.52 (dt, J = 8.7, 33.63,26.53, 23.59, 6.7 Hz, 1H), 3.16 (t, J = 9.0 Hz, 18.75, 18.12, 10.75 1H),3.05 (dd, J = 13.3, 3.3 Hz, 1H), 2.37-2.24 (m, 2H), 1.80 (ddt, J = 12.1,8.3, 3.9 Hz, 1H), 1.64 (dt, J = 14.0, 7.0 Hz, 3H), 1.64-1.54 (m, 1H),1.54-1.41 (m, 1H), 1.47 (d, J = 6.4 Hz, 3H), 1.32-1.19 (m, 1H), 0.99 (d,J = 7.3 Hz, 3H), 0.94-0.79 (m, 1H) F34 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ12.09 (d, J = 0.7 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.47 (d, J =8.2 Hz, 172.16, 168.62, 3367, ([M]⁺) 1H), 7.98 (d, J = 5.2 Hz, 155.32,154.60, 2941, calcd for 1H), 7.31 (dd, J = 2.0, 0.8 Hz, 148.70, 141.04,2874, C₂₅H₃₄N₂O₇, 1H), 6.89-6.83 (m, 1H), 140.52, 130.40, 1741,474.2366; 6.28 (dd, J = 3.1, 1.9 Hz, 1H), 110.11, 109.45, 1649, found,6.02 (d, J = 3.1 Hz, 1H), 4.94 (dq, J = 9.2, 106.08, 83.43, 80.26, 1528,474.2394 6.4 Hz, 1H), 4.56 (ddd, 75.45, 56.06, 51.48, 1056 J = 10.9,8.2, 6.9 Hz, 1H), 43.15, 33.52, 29.35, 3.94 (s, 3H), 3.50 (dd, J = 8.4,6.5 Hz, 29.21, 27.93, 19.48, 1H), 3.31 (dd, J = 8.4, 6.3 Hz, 19.46,18.84, 18.18 1H), 3.15 (t, J = 9.0 Hz, 1H), 3.01 (dd, J = 14.6, 3.5 Hz,1H), 2.52 (dd, J = 14.6, 11.2 Hz, 1H), 2.35-2.22 (m, 1H), 1.96 (ddt, J =14.8, 6.8, 3.5 Hz, 1H), 1.86 (dq, J = 13.2, 6.6 Hz, 1H), 1.71-1.49 (m,3H), 1.45 (d, J = 6.4 Hz, 3H), 1.39-1.28 (m, 1H), 1.07-0.95 (m, 1H),0.94 (d, J = 6.7 Hz, 6H) F35 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (s,¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.48 (d, J = 8.1 Hz, 1H), 176.47,172.25, 3388, ([M]⁺) 7.99 (d, J = 5.2 Hz, 1H), 168.63, 155.35, 2957,calcd for 6.87 (d, J = 5.2 Hz, 1H), 5.03 (dq, J = 9.5, 148.74, 140.50,1730, C₂₆H₃₈N₂O₇, 6.4 Hz, 1H), 4.86 (t, J = 9.1 Hz, 130.39, 109.47,73.59, 1649, 490.2679; 1H), 4.59 (ddd, J = 10.9, 56.07, 51.49, 40.61,1525, found, 8.1, 7.0 Hz, 1H), 3.94 (s, 36.99, 36.50, 34.29, 1146490.2689 3H), 2.58 (hept, J = 7.0 Hz, 33.68, 33.47, 31.85, 1H),2.44-2.32 (m, 1H), 27.24, 25.03, 25.01 1.93-0.87 (m, 26H) 19.11, 18.95,18.78, 17.50 F36 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (s, ¹³C NMR(CDCl₃) δ Film) (m/z) 1H), 8.51 (d, J = 8.1 Hz, 1H), 172.25, 168.61,3323, ([M]⁺) 7.98 (d, J = 5.2 Hz, 1H), 155.29, 148.67, 2941, calcd for6.86 (d, J = 5.2 Hz, 1H), 4.89 (dq, J = 9.3, 140.50, 130.40, 2869,C₂₅H₃₈N₂O₆, 6.4 Hz, 1H), 4.55 (ddd, 109.44, 84.49, 75.64, 1736,462.2730; J = 10.8, 8.3, 7.0 Hz, 1H), 75.34, 56.04, 51.53, 1650, found,3.94 (s, 3H), 3.64 (dt, J = 8.6, 6.5 Hz, 42.19, 37.25, 36.80, 1532,462.2738 1H), 3.44 (dt, J = 8.7, 6.8 Hz, 33.93, 33.60, 31.77, 1190 1H),3.01 (t, J = 8.9 Hz, 27.51, 25.09, 25.07, 1H), 2.34 (dt, J = 13.4, 6.9Hz, 23.53, 18.94, 18.10, 1H), 1.91-1.22 (m, 18H), 10.73 1.18-0.98 (m,4H), 0.94 (t, J = 7.4 Hz, 3H) F37 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ12.11 (d, J = 0.6 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.51 (d, J =8.2 Hz, 172.25, 168.61, 3342, ([M]⁺) 1H), 7.98 (d, J = 5.2 Hz, 155.29,148.67, 2946, calcd for 1H), 6.86 (d, J = 5.2 Hz, 1H), 140.50, 130.41,2869, C₂₆H₄₀N₂O₆, 4.89 (dq, J = 9.4, 6.5 Hz, 1H), 109.44, 84.21, 80.40,1738, 476.2886; 4.55 (ddd, J = 10.8, 8.2, 7.0 Hz, 75.70, 56.04, 51.54,1648, found, 1H), 3.94 (s, 3H), 42.21, 37.21, 36.70, 1189, 476.28903.81-3.60 (m, 1H), 3.47 (dd, J = 8.4, 33.96, 33.60, 31.72, 1054 6.0 Hz,1H), 3.25 (dd, J = 8.4, 29.19, 27.50, 25.08, 6.7 Hz, 1H), 2.99 (t, J =8.8 Hz, 25.07, 19.54, 19.43, 1H), 2.34 (dt, J = 13.0, 6.6 Hz, 18.96,18.15 1H), 1.93-1.21 (m, 16H), 1.20-0.84 (m, 10H) F38 160-163 — HRMS-ESI¹H NMR (CDCl₃) δ 12.08 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.52 (d, J = 8.1Hz, 1H), 172.23, 168.64, [M + H]⁺ 8.00 (d, J = 5.2 Hz, 1H), 159.64,155.34, calcd for 7.34-7.23 (m, 2H), 6.96 (dd, J = 7.9, 148.71, 140.54,C₂₃H₂₉N₂O₆, 3.7 Hz, 3H), 6.87 (d, J = 5.2 Hz, 130.39, 129.61, 429.2020;1H), 5.12 (dq, J = 9.1, 121.04, 115.48, found, 6.4 Hz, 1H), 4.61 (dt, J= 11.0, 109.47, 82.22, 74.96, 429.2028 7.1 Hz, 1H), 4.18 (t, J = 8.8 Hz,56.08, 51.60, 37.65, 1H), 3.94 (s, 3H), 2.40 (dt, 33.55, 32.29, 19.19, J= 13.3, 6.7 Hz, 1H), 18.31, 17.75 1.99-1.87 (m, 1H), 1.73 (ddt, J =19.3, 12.4, 6.2 Hz, 3H), 1.52-1.39 (m, 1H), 1.33 (d, J = 6.5 Hz, 3H),1.28 (dt, J = 10.5, 5.2 Hz, 1H), 1.02 (d, J = 6.9 Hz, 3H) F39 129-130 —HRMS-ESI ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.50(d, J = 8.1 Hz, 1H), 172.27, 168.64, [M + H]⁺ 7.99 (d, J = 5.2 Hz, 1H),155.33, 148.71, calcd for 7.35 (d, J = 3.8 Hz, 5H), 6.86 (d, J = 5.2 Hz,140.53, 138.00, C₂₄H₃₁N₂O₆, 1H), 4.97 (dq, J = 9.1, 130.43, 128.48,443.2177; 6.4 Hz, 1H), 4.72 (d, J = 10.8 Hz, 127.84, 127.73, found, 1H),4.64-4.54 (m, 109.46, 85.25, 75.60, 443.2171 2H), 3.94 (s, 3H), 3.24 (t,J = 8.9 Hz, 75.45, 56.07, 51.56, 1H), 2.36 (dt, J = 13.3, 37.94, 33.61,32.24, 6.7 Hz, 1H), 1.84-1.55 (m, 19.07, 18.23, 17.79 4H), 1.49 (d, J =6.4 Hz, 3H), 1.41 (dt, J = 13.3, 10.8 Hz, 1H), 1.22-1.16 (m, 1H), 1.08(d, J = 6.8 Hz, 3H) F40 — — ESIMS ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR(CDCl₃) δ m/z 429.3 1H), 8.46 (d, J = 8.2 Hz, 1H), 172.06, 168.65, ([M +H]⁺) 7.98 (d, J = 5.2 Hz, 1H), 155.36, 148.72, 7.30 (dd, J = 8.4, 6.3Hz, 2H), 140.53, 140.45, 7.21 (td, J = 7.2, 6.7, 1.5 Hz, 3H), 130.37,128.86, 6.86 (d, J = 5.3 Hz, 1H), 128.55, 126.17, 4.90 (dq, J = 9.3, 6.3Hz, 1H), 109.48, 76.11, 74.90, 4.58 (ddd, J = 10.9, 8.2, 7.1 Hz, 56.08,51.35, 47.48, 1H), 3.94 (s, 3H), 3.56 (td, J = 9.0, 37.78, 33.51, 26.97,8.5, 2.7 Hz, 1H), 3.13 (dd, 18.89, 18.14 J = 13.5, 4.5 Hz, 1H), 2.48(dd, J = 13.5, 10.5 Hz, 1H), 2.33 (dt, J = 14.0, 7.2 Hz, 1H), 1.85-1.73(m, 2H), 1.72-1.51 (m, 3H), 1.44 (d, J = 6.3 Hz, 3H), 1.36-1.24 (m, 1H),1.04-0.91 (m, 1H) F41 129-131 — ESIMS ¹H NMR (CDCl₃) δ 12.10 (s, ¹³C NMR(CDCl₃) δ m/z 499 1H), 8.45 (d, J = 8.2 Hz, 1H), 172.16, 168.63, ([M +H]⁺) 8.03-7.89 (m, 1H), 155.32, 148.70, 7.12-7.02 (m, 4H), 6.85 (d, J =5.2 Hz, 140.52, 137.60, 1H), 4.93 (dq, J = 9.2, 6.4 Hz, 135.37, 130.40,1H), 4.62-4.50 (m, 1H), 129.06, 128.72, 3.92 (s, 3H), 3.56 (dd, J = 8.4,109.46, 83.67, 80.66, 6.2 Hz, 1H), 3.34 (dd, J = 8.4, 75.57, 56.06,51.46, 6.5 Hz, 1H), 3.15 (t, J = 9.0 Hz, 46.15, 36.24, 33.61, 1H), 3.07(dd, J = 13.3, 29.28, 26.50, 21.04, 3.2 Hz, 1H), 2.38-2.24 (m, 19.56,19.50, 18.77, 5H), 1.97-1.78 (m, 2H), 18.19 1.68-1.54 (m, 2H), 1.54-1.40(m, 4H), 1.25 (dtd, J = 13.2, 10.6, 2.2 Hz, 1H), 0.97 (d, J = 6.7 Hz,3H), 0.96 (d, J = 6.7 Hz, 3H), 0.92-0.81 (m, 1H) F42 — — ESIMS ¹H NMR(CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ m/z 497 1H), 8.45 (d, J = 8.2 Hz,1H), 172.13, 168.62, ([M + H]⁺) 7.97 (d, J = 5.2 Hz, 1H), 155.32,148.70, 7.14-7.03 (m, 4H), 6.85 (d, J = 5.2 Hz, 140.52, 137.47, 1H),4.94 (dq, J = 9.2, 6.4 Hz, 135.39, 130.38, 1H), 4.56 (ddd, J = 10.9,129.07, 128.73, 8.3, 7.0 Hz, 1H), 3.93 (s, 3H), 109.46, 83.75, 78.75,3.58 (dd, J = 9.7, 7.0 Hz, 1H), 75.51, 56.06, 51.43, 3.45 (dd, J = 9.7,6.8 Hz, 1H), 46.01, 36.39, 33.60, 3.18 (t, J = 9.0 Hz, 1H), 26.54,21.03, 18.71, 3.11 (dd, J = 13.2, 3.3 Hz, 1H), 18.11, 11.18, 3.16,2.37-2.23 (m, 5H), 3.02 1.93-1.82 (m, 1H), 1.66-1.53 (m, 2H), 1.53-1.41(m, 4H), 1.31-1.20 (m, 1H), 1.18-1.08 (m, 1H), 0.93-0.83 (m, 1H),0.62-0.55 (m, 2H), 0.29-0.22 (m, 2H) F43 — — HRMS-ESI ¹H NMR (CDCl₃) δ¹³C NMR (CDCl₃) δ (m/z) 12.19-11.98 (m, 1H), 8.50 (d, J = 8.2 Hz,172.18, 168.63, [M + H]⁺ 1H), 7.99 (d, J = 5.2 Hz, 155.34, 148.71, calcdfor 1H), 6.87 (d, J = 5.2 Hz, 1H), 140.54, 130.40, C₂₂H₃₄N₂O₆, 4.91 (dt,J = 9.1, 6.4 Hz, 1H), 109.46, 83.79, 82.16, 441.2395; 4.63-4.52 (m, 2H),80.24, 75.52, 56.08, found, 4.52-4.39 (m, 1H), 3.94 (s, 3H), 51.52,39.76, 33.48, 441.2411 3.45 (dd, J = 8.3, 6.6 Hz, 1H), 31.59, 31.39,29.17, 3.26 (dd, J = 8.4, 6.4 Hz, 1H), 28.64, 19.45, 19.41, 3.08 (t, J =8.6 Hz, 1H), 19.12, 18.14 2.35 (dt, J = 13.3, 6.6 Hz, 1H), 2.16-1.95 (m,1H), 1.92-1.79 (m, 1H), 1.79-1.60 (m, 4H), 1.60-1.52 (m, 1H), 1.43 (d, J= 6.4 Hz, 3H), 1.42-1.34 (m, 1H), 1.11 (dd, J = 14.9, 5.2 Hz, 1H), 0.92(dd, J = 6.7, 0.7 Hz, 6H) F44 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR(CDCl₃) δ (m/z) 12.17-11.97 (m, 1H), 8.52 (d, J = 8.1 Hz, 172.16,168.66, [M + H]⁺ 1H), 8.00 (d, J = 5.2 Hz, 159.31, 158.75, calcd for1H), 7.37-7.27 (m, 2H), 155.35, 148.72, C₃₀H₃₅N₂O₇, 7.25-7.20 (m, 2H),7.03-6.78 (m, 140.56, 130.37, 535.2439; 7H), 5.13 (dt, J = 9.1, 6.5 Hz129.71, 129.40, found, 1H), 4.69-4.56 (m, 1H), 121.23, 120.64, 535.24594.30 (t, J = 8.7 Hz, 1H), 3.95 (d, J = 7.6 Hz, 115.40, 114.44, 5H), 2.41(dt, J = 12.7, 109.49, 81.08, 75.04, 6.5 Hz, 1H), 2.17-2.02 (m, 66.00,56.08, 51.56, 2H), 2.02-1.86 (m, 1H), 40.19, 37.62, 33.51, 1.86-1.64 (m,3H), 1.45 (q, J = 11.1 Hz, 30.50, 28.39, 19.25, 1H), 1.34 (d, J = 6.5Hz, 18.35 3H), 1.31-1.20 (m, 1H) F45 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.08(s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.52 (d, J = 8.1 Hz, 1H), 171.49,167.99, [M + H]⁺ 8.00 (d, J = 5.2 Hz, 1H), 158.77, 154.70, calcd for7.33-7.27 (m, 2H), 6.94 (dd, J = 7.9, 148.07, 139.89, C₂₅H₃₃N₂O₇, 5.5Hz, 3H), 6.87 (d, J = 5.2 Hz, 129.73, 128.98, 473.2282; 1H), 5.19-5.01(m, 120.45, 114.72, found, 1H), 4.61 (dt, J = 10.9, 7.1 Hz, 108.83,80.40, 74.44, 473.2297 1H), 4.25 (t, J = 8.8 Hz, 1H), 70.13, 57.80,55.42, 3.95 (s, 3H), 3.38 (t, J = 6.4 Hz, 50.89, 39.47, 32.90, 2H), 3.27(s, 3H), 2.40 (dt, 29.89, 27.44, 18.46, J = 12.8, 6.5 Hz, 1H), 17.702.02-1.80 (m, 3H), 1.80-1.60 (m, 2H), 1.56-1.37 (m, 2H), 1.31 (d, J =6.5 Hz, 3H), 1.19 (dd, J = 14.7, 7.8 Hz, 1H) F46 — — HRMS-ESI ¹H NMR(CDCl₃) δ 12.09 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.52 (d, J= 8.1 Hz, 172.14, 168.61, ([M + Na]⁺) 1H), 7.98 (d, J = 5.2 Hz, 155.28,148.65, calcd for 1H), 6.87 (d, J = 5.2 Hz, 1H), 140.50, 130.35,C₂₃H₃₆N₂O₆SNa, 4.91 (dq, J = 9.1, 6.4 Hz, 1H), 109.45, 83.85, 80.36,491.2186; 4.64-4.50 (m, 1H), 3.94 (s, 75.55, 56.03, 51.48, found, 3H),3.46 (dd, J = 8.4, 6.5 Hz, 42.19, 33.42, 32.10, 491.2199 1H), 3.28 (dd,J = 8.4, 6.4 Hz, 29.90, 29.17, 29.02, 1H), 3.05 (t, J = 8.8 Hz, 1H),27.74, 25.25, 19.45, 2.59 (ddd, J = 12.9, 9.6, 4.6 Hz, 18.91, 18.12,15.33 1H), 2.44 (ddd, J = 12.7, 9.0, 7.3 Hz, 1H), 2.35 (dt, J = 12.9,6.7 Hz, 1H), 2.10 (s, 3H), 1.95 (dddd, J = 12.5, 9.8, 6.0, 3.0 Hz, 1H),1.85 (dt, J = 13.2, 6.6 Hz, 1H), 1.80-1.58 (m, 4H), 1.58-1.46 (m, 2H),1.43 (d, J = 6.4 Hz, 3H), 1.06 (ddd, J = 11.4, 6.3, 3.2 Hz, 1H), 0.93(dd, J = 6.7, 0.9 Hz, 6H) F47 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.10 (d, J= 0.5 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.50 (d, J = 8.1 Hz, 172.22,168.61, [M + H]⁺ 1H), 7.99 (d, J = 5.2 Hz, 155.33, 148.70, calcd for1H), 6.86 (d, J = 5.2 Hz, 1H), 140.52, 130.42, C₂₃H₃₆O₇Na, 4.90 (dq, J =9.1, 6.4 Hz, 1H), 109.44, 83.97, 80.37, 475.2415; 4.56 (ddd, J = 10.8,8.1, 7.0 Hz, 75.65, 71.25, 58.52, found, 1H), 3.94 (s, 3H), 3.42 (q,56.07, 51.53, 40.24, 475.2836 J = 6.7, 6.3 Hz, 3H), 3.33 (s, 33.56,30.39, 29.17, 3H), 3.32-3.26 (m, 1H), 28.30, 19.51, 19.42, 3.05 (t, J =8.8 Hz, 1H), 2.35 (dt, J = 13.2, 19.04, 18.16 6.5 Hz, 1H), 2.05-1.91 (m,1H), 1.91-1.78 (m, 1H), 1.78-1.62 (m, 3H), 1.59-1.45 (m, 2H), 1.43 (d, J= 6.4 Hz, 3H), 1.40-1.32 (m, 1H), 1.11-1.02 (m, 1H), 0.92 (dd, J = 6.7,2.7 Hz, 6H) F48 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.11 (d, J = 0.5 Hz, ¹³CNMR (CDCl₃) δ (m/z) 1H), 8.50 (d, J = 8.1 Hz, 172.26, 168.61, [M + H]⁺1H), 7.99 (d, J = 5.2 Hz, 155.32, 148.69, calcd for 1H), 6.86 (d, J =5.2 Hz, 1H), 140.52, 130.44, C₂₂H₃₅O₆N₂, 4.90 (dq, J = 9.2, 6.4 Hz, 1H),109.43, 84.18, 80.43, 423.2490; 4.62-4.48 (m, 1H), 3.94 (s, 75.72,56.07, 51.53, found, 3H), 3.43 (dd, J = 8.4, 6.6 Hz, 45.18, 33.64,29.18, 423.2500 1H), 3.27 (dd, J = 8.4, 6.4 Hz, 27.05, 23.25, 19.50,1H), 3.02 (t, J = 8.9 Hz, 1H), 19.45, 18.74, 18.19, 2.34 (dt, J = 13.1,6.9 Hz, 1H), 11.96 1.92-1.80 (m, 1H), 1.73 (dtt, J = 15.4, 7.5, 3.5 Hz,2H), 1.61 (dd, J = 14.8, 7.1 Hz, 1H), 1.55-1.45 (m, 1H), 1.42 (d, J =6.4 Hz, 4H), 1.40-1.32 (m, 1H), 1.28-1.17 (m, 1H), 1.06-0.96 (m, 1H),0.94-0.88 (m, 9H) F49 62-66 — ESIMS ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR(CDCl₃) δ m/z 519 1H), 8.48 (d, J = 8.2 Hz, 1H), 172.06, 168.59, ([M +H]⁺) 7.98 (d, J = 5.1 Hz, 1H), 159.58, 155.27, 7.37-7.28 (m, 2H),7.12-6.93 (m, 148.66, 140.47, 7H), 6.86 (d, J = 5.2 Hz, 1H), 136.92,135.38, 5.14 (dq, J = 9.2, 6.4 Hz, 1H), 130.28, 129.63, 4.62 (dt, J =10.9, 7.4 Hz, 1H), 128.98, 128.59, 4.35 (t, J = 8.9 Hz, 1H), 121.16,115.48, 3.93 (s, 3H), 2.99 (dd, J = 13.3, 3.2 Hz, 109.43, 81.02, 74.89,1H), 2.42-2.26 (m, 5H), 55.99, 51.43, 45.59, 2.16-2.04 (m, 1H), 36.34,33.47, 26.57, 1.79-1.52 (m, 3H), 1.41-1.23 (m, 20.95, 18.78, 18.33 4H),1.08-0.98 (m, 1H) F50 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ(m/z) 12.27-11.86 (m, 1H), 8.53 (d, J = 8.1 Hz, 172.08, 168.68, [M + H]⁺1H), 8.00 (d, J = 5.2 Hz, 159.15, 155.37, calcd for 1H), 7.37-7.27 (m,2H), 148.74, 140.58, C₂₄H₃₀O₆BrN₂, 7.04-6.92 (m, 3H), 6.88 (d, J = 5.2Hz, 130.35, 129.77, 521.1282; 1H), 5.13 (dq, J = 9.1, 6.5 Hz, 121.39,115.38, found, 1H), 4.62 (ddd, J = 10.9, 109.52, 80.87, 74.94, 521.12838.0, 6.8 Hz, 1H), 4.25 (t, J = 8.7 Hz, 56.09, 51.57, 41.28, 1H), 3.95(s, 3H), 34.14, 33.37, 31.47, 3.46 (ddd, J = 10.0, 7.3, 5.0 Hz, 28.22,19.16, 18.29 1H), 3.35 (ddd, J = 10.0, 8.3, 6.9 Hz, 1H), 2.50-2.33 (m,1H), 2.10 (m, 2H), 1.94-1.78 (m, 2H), 1.73 (dt, J = 15.8, 8.0 Hz, 2H),1.54-1.40 (m, 1H), 1.33 (d, J = 6.5 Hz, 3H), 1.30-1.18 (m, 1H) 51 — —HRMS-ESI ¹H NMR (CDCl₃) δ 12.08 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ (m/z)1H), 8.52 (d, J = 8.1 Hz, 172.20, 168.65, [M + H]⁺ 1H), 8.00 (d, J = 5.2Hz, 159.64, 155.35, calcd for 1H), 7.34-7.27 (m, 2H), 148.73, 140.54,C₂₄H₃₁O₆N₂, 7.01-6.91 (m, 3H), 6.87 (d, J = 5.2 Hz, 130.41, 129.61,443.2177; 1H), 5.10 (dq, J = 9.1, 6.5 Hz, 121.00, 115.40, found, 1H),4.61 (ddd, J = 10.8, 109.48, 81.38, 75.11, 443.2186 8.0, 7.1 Hz, 1H),4.23 (t, J = 8.8 Hz, 56.08, 51.56, 44.97, 1H), 3.94 (s, 3H), 33.61,26.99, 23.52, 2.47-2.33 (m, 1H), 1.95-1.83 (m, 18.80, 18.39, 11.87 1H),1.78-1.59 (m, 4H), 1.50-1.38 (m, 1H), 1.31 (d, J = 6.5 Hz, 3H),1.28-1.21 (m, 1H), 1.21-1.10 (m, 1H), 0.88 (t, J = 7.3 Hz, 3H) F52 68-72— ESIMS ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ m/z 555 1H), 8.46(d, J = 8.2 Hz, 1H), 172.03, 168.60, ([M + H]⁺) 7.98 (d, J = 5.2 Hz,1H), 161.32 (dd, J = 247.2, 12.6 Hz), 7.42-7.28 (m, 5H), 7.09 (td, J =8.7, 161.06 (dd, J = 247.1, 6.6 Hz, 1H), 6.86 (d, J = 5.3 Hz, 11.6 Hz),1H), 6.83-6.72 (m, 155.28, 148.66, 2H), 5.01 (dq, J = 9.2, 6.4 Hz,140.48, 137.70, 1H), 4.82 (d, J = 10.9 Hz, 1H), 131.77-131.21 (m),130.30, 4.64 (d, J = 10.9 Hz, 1H), 128.48, 127.88, 4.59 (dt, J = 10.9,7.4 Hz, 1H), 127.60, 123.02 (dd, J = 16.0, 3.93 (s, 3H), 3.42 (t, J =9.0 Hz, 3.9 Hz), 1H), 3.10-2.99 (m, 1H), 111.04 (dd, J = 20.9, 3.6 Hz),2.51 (dd, J = 13.5, 11.5 Hz, 1H), 109.43, 2.32 (dtd, J = 13.2, 6.6, 2.0Hz, 104.17-103.09 (m), 83.83, 1H), 1.95 (ddq, J = 12.0, 7.8, 75.34,75.17, 56.00, 3.8 Hz, 1H), 1.74-1.40 (m, 51.38, 44.42, 33.44, 6H),1.34-1.22 (m, 1H), 29.25, 27.07, 18.77, 1.02-0.90 (m, 1H) 18.20 ¹⁹F NMR(CDCl₃) δ −113.21 (d, J = 6.7 Hz), −113.59 (d, J = 6.8 Hz) F53 — —HRMS-ESI ¹H NMR (CDCl₃) δ 12.06 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ (m/z)1H), 8.54 (d, J = 8.1 Hz, 172.08, 168.69, [M + H]⁺ 1H), 8.03 (d, J = 5.2Hz, 158.89, 155.37, calcd for 1H), 7.42-7.30 (m, 2H), 148.74, 140.59,C₂₄H₂₉O₆N₂F₂, 7.05-6.99 (m, 1H), 6.99-6.94 (m, 130.32, 129.86, 479.1988;2H), 6.90 (d, J = 5.1 Hz, 1H), 121.62, 116.72 (t, J = 239 hz), found,6.09-5.68 (m, 1H), 5.15 (dq, 115.25, 479.1989 J = 9.2, 6.5 Hz, 1H),109.53, 80.51, 74.76, 4.65 (ddd, J = 11.0, 8.1, 6.9 Hz, 56.09, 51.54,35.73 (t, 1H), 4.27 (t, J = 8.7 Hz, 1H), J = 21 Hz), 33.31, 3.97 (s,3H), 2.45 (dt, J = 13.2, 29.34, 19.25, 18.27 6.7 Hz, 1H), 2.12 (dt, J =8.7, 3.7 Hz, 1H), 2.04 (ddt, J = 14.5, 9.1, 4.6 Hz, 1H), 1.88 (dddd, J =22.5, 14.7, 11.4, 7.1 Hz, 3H), 1.77-1.65 (m, 1H), 1.48 (q, J = 11.1 Hz,1H), 1.35 (d, J = 6.5 Hz, 3H), 1.33-1.25 (m, 1H) F54 — — HRMS-ESI ¹H NMR(CDCl₃) δ 12.09 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.49 (d, J= 8.1 Hz, 172.18, 168.62, [M + H]⁺ 1H), 7.99 (d, J = 5.2 Hz, 155.32,148.70, calcd for 1H), 6.86 (d, J = 5.1 Hz, 1H), 140.52, 130.41,C₂₆H₃₉O₇N₂, 4.91 (dq, J = 9.1, 6.4 Hz, 1H), 109.44, 83.96, 78.39,491.2752; 4.66-4.47 (m, 1H), 3.94 (s, 75.59, 75.48, 69.09, found, 3H),3.55-3.37 (m, 4H), 56.07, 51.48, 40.49, 491.2758 3.36-3.17 (m, 2H), 3.09(t, J = 8.9 Hz, 33.58, 30.66, 28.15, 1H), 2.35 (dt, J = 13.3, 6.6 Hz,18.97, 18.10, 11.09, 1H), 2.08-1.93 (m, 1H), 10.66, 3.18, 3.02, 2.95,1.70 (tq, J = 13.2, 7.3, 5.3 Hz, 2.90 3H), 1.60-1.47 (m, 2H), 1.44 (d, J= 6.5 Hz, 3H), 1.42-1.31 (m, 1H), 1.17-0.94 (m, 3H), 0.54 (dddd, J =10.0, 8.0, 4.1, 2.8 Hz, 4H), 0.32-0.13 (m, 4H) 55 66-70 — ESIMS ¹H NMR(CDCl₃) δ 12.09 (s, ¹³C NMR (CDCl₃) δ m/z 553 1H), 8.45 (d, J = 8.2 Hz,1H), 172.04, 168.57, ([M + H]⁺) 8.00-7.93 (m, 1H), 7.10 (d, J = 7.8 Hz,155.26, 148.64, 2H), 7.04 (d, J = 8.0 Hz, 140.46, 137.13, 2H), 6.85 (d,J = 5.2 Hz, 135.46, 130.28, 1H), 4.92 (dq, J = 9.2, 6.4 Hz, 129.05,128.57, 1H), 4.61-4.50 (m, 1H), 131.35-122.86 (m), 109.41, 3.92 (s, 3H),3.80 (dt, J = 8.9, 6.1 Hz, 84.15, 75.08, 71.62, 1H), 3.61 (dt, J = 8.8,6.2 Hz, 55.98, 51.37, 45.75, 1H), 3.18 (t, J = 9.0 Hz, 36.42, 33.46,30.71 (q, 1H), 2.97 (dd, J = 13.3, 3.5 Hz, J = 29.1 Hz) 26.60, 1H),2.41-2.13 (m, 7H), 23.01 (q, J = 3.1 Hz), 1.91-1.76 (m, 3H), 20.93,18.69, 18.04 1.69-1.40 (m, 6H), 1.33-1.20 (m, ¹⁹F NMR (CDCl₃) δ −66.331H), 0.93-0.82 (m, 1H) F56 — — ESIMS ¹H NMR (CDCl₃) δ 12.09 (s, ¹³C NMR(CDCl₃) δ m/z 583 1H), 8.46 (d, J = 8.2 Hz, 1H), 172.04, 168.58, ([M +H]⁺) 7.97 (d, J = 5.2 Hz, 1H), 162.89-159.93 (m) 7.32-7.07 (m, 6H),6.88-6.74 (m, 161.08 (dd J = 247.0, 11.6 Hz), 3H), 4.94 (dq, J = 9.2,6.4 Hz, 155.27, 148.65 1H), 4.56 (dt, J = 10.9, 7.5 Hz, 141.66, 140.46,1H), 3.92 (s, 3H), 3.79 (dt, J = 8.8, 131.49 (dd, J = 9.4, 6.5 Hz), 6.3Hz, 1H), 3.58 (dt, J = 8.9, 130.31, 128.32, 6.5 Hz, 1H), 3.19 (t, J =9.0 Hz, 128.27, 125.83, 1H), 2.99 (d, J = 13.2 Hz, 123.13 (dd, J = 15.9,3.7 Hz), 1H), 2.74 (td, J = 7.5, 3.7 Hz, 111.02 (dd, J = 20.9, 2H), 2.48(dd, J = 13.6, 3.7 Hz), 109.42, 11.5 Hz, 1H), 2.31 (dt, J = 12.7,104.28-102.96 (m), 6.7 Hz, 1H), 83.96, 75.25, 72.90, 2.03-1.80 (m, 3H),1.72-1.37 (m, 6H), 56.00, 51.36, 44.44, 1.34-1.20 (m, 1H), 33.45, 32.35,31.88, 0.99-0.86 (m, 1H) 29.29, 27.04, 18.72, 18.07 ¹⁹F NMR (CDCl₃) δ−113.26 (d, J = 7.1 Hz), −113.60 (d, J = 6.9 Hz) F57 — — HRMS-ESI ¹H NMR(CDCl₃) δ 12.08 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.49 (d, J = 8.0 Hz,1H), 172.15, 168.63, [M + H]⁺ 7.99 (d, J = 5.2 Hz, 1H), 158.82, 155.32,calcd for 7.37-7.27 (m, 2H), 6.99-6.80 (m, 148.70, 140.53, C₂₈H₃₇O₇N₂,4H), 5.06-4.87 (m, 1H), 130.39, 129.43, 513.2595; 4.57 (dt, J = 10.8,7.2 Hz, 1H), 120.62, 114.46, found, 4.09-3.98 (m, 2H), 3.94 (s, 3H),109.45, 83.88, 78.27, 513.2605 3.57-3.35 (m, 2H), 3.15 (t, J = 8.9 Hz,75.52, 66.14, 56.07, 1H), 2.35 (dt, J = 13.1, 51.47, 40.30, 33.54, 6.6Hz, 1H), 2.21 (dq, J = 10.4, 30.31, 28.11, 19.03, 3.8 Hz, 1H), 1.81 (dd,18.11, 11.08, 3.16, J = 11.2, 5.8 Hz, 2H), 2.94 1.79-1.66 (m, 2H), 1.61(d, J = 10.7 Hz, 1H), 1.45 (d, J = 6.4 Hz, 3H), 1.44-1.33 (m, 1H), 1.08(dq, J = 12.4, 6.3, 5.4 Hz, 2H), 0.55 (dt, J = 8.0, 4.6 Hz, 2H), 0.21(q, J = 5.1 Hz, 2H) F58 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.09 (d, J = 0.6Hz, 13C NMR (151 MHz, (m/z) 1H), 8.58 (d, J = 7.7 Hz, CDCl₃) 173.09,[M + H]⁺ 1H), 7.99 (d, J = 5.2 Hz, 168.55, 155.35, calcd for 1H), 6.87(d, J = 5.1 Hz, 1H), 148.74, 140.54, C₁₈H₂₅O₆N₂, 5.02 (dq, J = 9.5, 6.3Hz, 1H), 130.44, 109.46, 86.83, 365.1707; 4.52 (ddd, J = 12.0, 7.9, 5.2Hz, 73.59, 67.75, 56.08, found, 1H), 3.94 (s, 3H), 52.94, 39.75, 36.06,365.17012 3.82 (ddd, J = 8.6, 7.1, 3.4 Hz, 1H), 35.77, 32.40, 21.75,3.71 (td, J = 8.9, 5.3 Hz, 1H), 18.39 3.44 (dd, J = 9.5, 6.3 Hz, 1H),2.38 (dddd, J = 14.0, 11.4, 5.2, 1.9 Hz, 1H), 2.13-2.03 (m, 1H), 1.98(ddt, J = 14.7, 8.1, 3.3 Hz, 1H), 1.94-1.86 (m, 1H), 1.84-1.72 (m, 1H),1.71-1.60 (m, 1H), 1.56-1.48 (m, 2H), 1.47 (dd, J = 5.8, 2.1 Hz, 1H),1.44 (d, J = 6.3 Hz, 3H) F59 69-72 — ESIMS ¹H NMR (CDCl₃) δ 12.08 (s,¹³C NMR (CDCl₃) δ m/z 521 1H), 8.44 (d, J = 8.2 Hz, 1H), 172.03, 168.56,([M + H]⁺) 7.95 (d, J = 5.1 Hz, 1H), 161.27 (dd, J = 246.8, 12.2 Hz),7.11 (td, J = 8.5, 6.4 Hz, 1H), 162.42-159.71 (m), 155.25, 148.62, 6.84(d, J = 5.2 Hz, 1H), 140.45, 131.50 (dd, J = 9.2, 6.82-6.71 (m, 2H),4.91 (dq, J = 9.2, 6.6 Hz), 130.29, 6.4 Hz, 1H), 4.55 (dt, J = 10.9,123.20 (dd, J = 16.2, 7.5 Hz, 1H), 3.91 (s, 3H), 3.7 Hz), 111.00 (dd, J= 20.9, 3.54 (dd, J = 8.4, 6.3 Hz, 1H), 3.7 Hz), 3.31 (dd, J = 8.4, 6.5Hz, 1H), 109.40, 3.15 (t, J = 9.0 Hz, 1H), 103.99-103.17 (m), 83.45,3.04-2.93 (m, 1H), 2.46 (dd, J = 13.5, 80.36, 75.37, 55.98, 11.6 Hz,1H), 2.36-2.24 (m, 51.34, 44.65, 33.44, 1H), 1.94-1.77 (m, 2H), 29.16,29.10, 26.96, 1.70-1.51 (m, 2H), 1.45 (d, J = 6.4 Hz, 19.40, 19.38,18.70, 4H), 1.33-1.19 (m, 1H), 18.06 0.95 (dd, J = 6.7, 4.7 Hz, 7H) ¹⁹FNMR (CDCl₃) δ −113.36 (d, J = 6.4 Hz), −113.63 (d, J = 6.4 Hz) F60 93-97— ESIMS ¹H NMR (CDCl₃) δ 12.03 (d, J = 0.5 Hz, ¹³C NMR (CDCl₃) δ m/z 5591H), 8.43 (d, J = 8.1 Hz, 171.98, 168.58, [M + H]⁺ 1H), 7.95 (d, J = 5.2Hz, 161.44 (dd, J = 246.7, 11.8 Hz) 1H), 7.60 (dd, J = 1.8, 0.9 Hz,160.93 (dd, J = 247.6, 1H), 7.17 (dd, J = 3.5, 0.9 Hz, 11.8 Hz), 1H),7.04 (td, J = 8.4, 6.4 Hz, 158.10, 155.25, 1H), 6.84 (d, J = 5.2 Hz,1H), 148.63, 146.90, 6.75-6.65 (m, 2H), 6.51 (dd, 143.79, 140.44, J =3.5, 1.7 Hz, 1H), 5.21 (t, J = 9.2 Hz, 131.51 (dd, J = 9.4, 6.5 Hz),1H), 5.12 (dq, J = 9.5, 130.20, 122.32 (dd, J = 15.9, 6.2 Hz, 1H), 4.60(dt, J = 10.9, 3.7 Hz), 7.5 Hz, 1H), 3.91 (s, 3H), 118.60, 111.94, 2.72(dd, J = 13.9, 4.5 Hz, 110.89 (dd, J = 21.0, 3.6 Hz), 1H), 2.51 (dd, J =13.9, 10.3 Hz, 109.43, 103.64 (t, J = 25.6 Hz), 1H), 2.36 (dtd, J =13.3, 76.26, 73.31, 7.7, 6.7, 3.4 Hz, 1H), 55.97, 51.28, 42.53,2.20-2.08 (m, 1H), 1.77-1.54 (m, 33.25, 29.99, 27.24, 3H), 1.40-1.25 (m,4H), 18.61, 17.44 1.13-1.01 (m, 1H) ¹⁹F NMR (CDCl₃) δ −112.90 (d, J =6.8 Hz), −113.48 (d, J = 6.7 Hz) F61 — — HRMS-ESI ¹H NMR (CDCl₃) δ 12.07(s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.53 (d, J = 8.1 Hz, 1H), 172.22,168.65, [2M + Na]⁺ 7.35-7.22 (m, 3H), 6.93 (dd, 159.29, 155.35, calcdfor J = 7.4, 4.7 Hz, 3H), 6.87 (d, J = 5.2 Hz, 148.73, 140.56,C₄₈H₅₆N₄NaO₁₂, 1H), 5.79 (ddd, J = 17.2, 138.40, 130.37, 903.3787; 10.3,8.0 Hz, 1H), 129.51, 121.15, found, 5.17 (dq, J = 9.0, 6.4 Hz, 1H),116.30, 115.78, 903.3801 5.05 (d, J = 17.1 Hz, 1H), 4.97 (d, J = 10.4Hz, 109.49, 80.41, 74.75, 1H), 56.08, 51.59, 47.47, 4.71-4.55 (m, 1H),4.33 (t, J = 8.8 Hz, 33.55, 31.01, 19.70, 1H), 3.95 (s, 3H), 18.342.59-2.48 (m, 1H), 2.40 (dt, J = 12.2, 6.8 Hz, 1H), 1.92 (dt, J = 16.2,8.3 Hz, 1H), 1.86-1.68 (m, 2H), 1.53-1.41 (m, 1H), 1.36 (d, J = 6.4 Hz,4H) F62 67-69 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.56 (d, J = 8.0 Hz, ¹³CNMR (CDCl₃) δ 3383, (m/z) 1H), 8.34 (d, J = 5.5 Hz, 172.71, 168.89,2950, ([M]⁺) 1H), 7.33-7.24 (m, 2H), 162.40, 159.71, 1772, calcd for7.00 (d, J = 5.5 Hz, 1H), 159.43, 146.72, 1744, C₂₉H₃₈N₂O₇, 6.99-6.89(m, 3H), 5.13-5.01 (m, 141.42, 137.48, 1679, 526.2679; 1H), 4.61 (ddd, J= 10.8, 8.3, 129.57, 120.96, 1509, found, 6.9 Hz, 1H), 4.23-4.15 (m,115.49, 109.82, 81.64, 1197 526.2687 1H), 3.90 (s, 3H), 74.87, 56.29,51.66, 2.45-2.32 (m, 1H), 2.40 (s, 3H), 43.19, 36.41, 33.81, 1.91-1.30(m, 7H), 1.29 (d, J = 6.5 Hz, 28.28, 27.88, 27.64, 3H), 1.28-1.04 (m,4H), 23.03, 22.06, 20.75, 0.80 (d, J = 6.6 Hz, 3H), 18.92, 18.37 0.79(d, J = 6.6 Hz, 3H) F63 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.54 (d, J =8.2 Hz, ¹³C NMR (CDCl₃) δ 3380, (m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.71,168.87, 2949, ([M]⁺) 1H), 7.00 (d, J = 5.5 Hz, 162.36, 159.40, 1772,calcd for 1H), 4.95-4.82 (m, 1H), 146.70, 141.44, 1741, C₂₇H₄₀N₂O₇, 4.55(ddd, J = 10.7, 8.4, 7.0 Hz, 137.44, 109.78, 84.35, 1677, 504.2836; 1H),3.90 (s, 3H), 78.61, 75.40, 56.27, 1508, found, 3.56-3.32 (m, 2H),3.09-2.95 (m, 1H), 51.57, 43.56, 36.44, 1368, 504.2842 2.39 (s, 3H),2.38-2.24 (m, 33.88, 28.07, 27.40, 1196 1H), 1.81-1.43 (m, 6H), 23.02,22.22, 20.74, 1.41 (d, J = 6.4 Hz, 3H), 18.71, 18.08, 11.12, 1.36-0.92(m, 6H), 0.89 (d, J = 6.6 Hz, 3.08, 3.00 3H), 0.88 (d, J = 6.6 Hz, 3H),0.62-0.49 (m, 2H), 0.27-0.15 (m, 2H) F64 121-123 (Neat) HRMS-ESI ¹H NMR(CDCl₃) δ 8.54 (d, J = 8.7 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.33(d, J = 5.4 Hz, 172.75, 168.88, 2936, ([M]⁺) 1H), 7.00 (d, J = 5.5 Hz,162.35, 159.40, 1772, calcd for 1H), 4.93-4.78 (m, 1H), 146.70, 141.48,1742, C₂₆H₄₀N₂O₇, 4.56 (ddd, J = 10.7, 8.4, 7.0 Hz, 137.45, 109.76,84.57, 1678, 492.2836; 1H), 3.90 (s, 3H), 75.41, 56.27, 51.59, 1507,found, 3.69-3.56 (m, 1H), 3.51-3.39 (m, 1H), 43.50, 36.52, 33.89, 1368,492.2862 3.07-2.94 (m, 1H), 2.40 (s, 28.10, 27.54, 23.53, 1195 3H),2.38-2.25 (m, 1H), 23.02, 22.22, 20.74, 1.84-1.25 (m, 9H), 1.41 (d, J =6.5 Hz, 18.78, 18.09, 10.70 3H), 1.25-0.95 (m, 4H), 0.93 (t, J = 7.4 Hz,3H), 0.89 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) F65 60-62 (Neat)HRMS-ESI ¹H NMR (CDCl₃) δ 8.54 (d, J = 8.9 Hz, ¹³C NMR (CDCl₃) δ 3375,(m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.70, 168.87, 2951, ([M]⁺) 1H), 7.00(d, J = 5.5 Hz, 162.37, 159.41, 1772, calcd for 1H), 4.92-4.80 (m, 1H),146.70, 141.42, 1742, C₂₇H₃₉F₃N₂O₇, 4.56 (ddd, J = 10.7, 8.4, 7.0 Hz,137.46, 127.16 (q, J = 276.2 Hz), 1677, 560.2709; 1H), 3.90 (s, 3H),109.79, 1508, found, 3.78-3.68 (m, 1H), 3.61-3.49 (m, 1H), 84.83, 75.03,71.53, 1369, 560.2733 3.08-2.97 (m, 1H), 2.39 (s, 56.27, 51.58, 43.44,1196 3H), 2.38-2.27 (m, 1H), 36.48, 33.83, 30.81 (q, 2.27-2.11 (m, 2H),1.88-1.27 (m, J = 29.0 Hz), 28.19, 9H), 1.39 (d, J = 6.4 Hz, 3H), 28.07,27.52, 23.06 (d, 1.27-0.93 (m, 4H), J = 3.0 Hz), 22.95, 0.93-0.83 (m,6H) 22.17, 20.74, 18.79, 18.11 ¹⁹F NMR (CDCl₃) δ −66.44 F66 58-60 (Neat)HRMS-ESI ¹H NMR (CDCl₃) δ 8.54 (d, J = 8.3 Hz, ¹³C NMR (CDCl₃) δ 3380,(m/z) 1H), 8.33 (d, J = 5.4 Hz, 172.69, 168.87, 2942, ([M]⁺) 1H), 7.00(d, J = 5.5 Hz, 162.36, 159.41, 1772, calcd for 1H), 4.92-4.79 (m, 1H),146.70, 141.44, 1741, C₂₄H₃₆N₂O₇, 4.56 (ddd, J = 10.7, 8.5, 7.1 Hz,137.45, 109.78, 86.40, 1678, 464.2523; 1H), 3.90 (s, 3H), 3.50 (s, 3H),75.14, 61.18, 56.27, 1507, found, 2.99-2.87 (m, 1H), 2.40 (s, 51.55,43.52, 36.48, 1368, 464.2545 3H), 2.38-2.25 (m, 1H), 33.88, 28.24,28.15, 1196 1.83-1.27 (m, 7H), 1.41 (d, J = 6.4 Hz, 27.29, 23.08, 22.17,3H), 1.27-0.91 (m, 4H), 20.74, 18.72, 18.03 0.89 (d, J = 6.6 Hz, 3H),0.88 (d, J = 6.6 Hz, 3H) F67 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.50 (d,J = 8.4 Hz, ¹³C NMR (CDCl₃) δ 3378, (m/z) 1H), 8.32 (d, J = 5.4 Hz,172.57, 168.85, 2939, ([M]⁺) 1H), 7.18-7.07 (m, 2H), 162.38, 161.28 (d,J = 243.6 Hz), 1772, calcd for 7.04-6.90 (m, 3H), 159.40, 1742,C₂₉H₃₅FN₂O₇, 5.00-4.85 (m, 1H), 4.64-4.50 (m, 146.70, 141.38, 1678,542.2428; 1H), 3.89 (s, 3H), 137.45, 136.31 (d, J = 3.2 Hz), 1508,found, 3.63-3.51 (m, 1H), 3.50-3.37 (m, 1H), 130.14 (d, J = 7.7 Hz),1314, 542.2436 3.20-3.10 (m, 1H), 115.12 (d J = 21.1 Hz), 1199 3.14-3.04(m, 1H), 2.39 (s, 3H), 109.80, 2.39-2.20 (m, 2H), 83.72, 78.75, 75.18,1.90-1.75 (m, 1H), 1.65-1.49 (m, 56.27, 51.47, 46.14, 2H), 1.47-1.33 (m,1H), 36.04, 33.82, 26.63, 1.45 (d, J = 6.4 Hz, 3H), 20.73, 18.73, 18.06,1.25-1.05 (m, 2H), 0.96-0.80 (m, 11.16, 3.14, 2.99 1H), 0.65-0.51 (m,2H), ¹⁹F NMR (CDCl₃) δ −117.47 0.32-0.17 (m, 2H) F68 — (Neat) HRMS-ESI¹H NMR (CDCl₃) δ 8.53 (d, J = 8.4 Hz, ¹³C NMR (CDCl₃) δ 3375, (m/z) 1H),8.33 (d, J = 5.4 Hz, 172.59, 168.88, 2939, ([M]⁺) 1H), 7.35-7.27 (m,2H), 162.41, 161.31 (d, J = 243.6 Hz), 1742, calcd for 7.12-6.89 (m,8H), 159.55, 1676, C₃₁H₃₃FN₂O₇, 5.17-5.05 (m, 1H), 4.62 (ddd, J = 11.0,159.44, 146.71, 1508, 564.2272; 8.4, 6.9 Hz, 1H), 141.37, 137.50, 1197found, 4.36-4.26 (m, 1H), 3.90 (s, 3H), 135.84 (d, J = 3.2 Hz), 564.22803.02-2.91 (m, 1H), 2.40 (s, 130.11 (d, J = 7.8 Hz), 3H), 2.39-2.28 (m,2H), 129.72, 121.26, 2.12-1.99 (m, 1H), 1.74-1.60 (m, 115.47, 115.12 (d,J = 21.1 Hz), 2H), 1.60-1.46 (m, 1H), 109.83, 1.33 (d, J = 6.5 Hz, 3H),81.01, 74.62, 56.29, 1.30-1.23 (m, 1H), 1.09-0.96 (m, 51.57, 45.70,36.12, 1H) 33.77, 26.87, 20.75, 18.93, 18.34 ¹⁹F NMR (CDCl₃) δ −117.35F69 74-76 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.50 (d, J = 8.3 Hz, ¹³C NMR(CDCl₃) δ 3376, (m/z) 1H), 8.32 (d, J = 5.4 Hz, 172.47, 168.87, 2940,([M]⁺) 1H), 7.17-7.06 (m, 2H), 162.41, 161.36 (d, J = 243.8 Hz), 1770,calcd for 7.04-6.91 (m, 3H), 5.86 (tt, J = 55.1, 159.44, 1743,C₂₇H₃₁F₃N₂O₇, 3.9 Hz, 1H), 146.72, 141.32, 1676, 552.2083; 5.00-4.86 (m,1H), 4.63-4.51 (m, 137.49, 135.85 (d, J = 3.1 Hz), 1508, found, 1H),4.05-3.90 (m, 1H), 130.14 (d, J = 7.8 Hz), 1199 552.2081 3.89 (s, 3H),3.85-3.67 (m, 1H), 115.20 (d, J = 21.1 Hz), 3.30-3.20 (m, 1H), 113.88(t, J = 241.2 Hz), 3.10-2.98 (m, 1H), 2.39 (s, 3H), 109.85, 2.39-2.20(m, 2H), 85.51, 74.42, 72.59 (t, 1.89-1.76 (m, 1H), 1.68-1.36 (m, J =27.7 Hz), 56.29, 3H), 1.45 (d, J = 6.4 Hz, 3H), 51.46, 45.79, 35.92,1.30-1.11 (m, 1H), 33.72, 26.60, 20.74, 0.96-0.81 (m, 1H) 18.82, 18.12¹⁹F NMR (CDCl₃) δ −117.20, −125.46 (d, J = 9.5 Hz, 2F) F70 — — ESIMS ¹HNMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 527.5 8.63-8.40 (m, 1H), 8.32 (d, J= 5.5 Hz, 172.64, 168.91, ([M + H]⁺) 1H), 7.32-7.25 (m, 2H), 162.38,159.41, 7.22-7.13 (m, 3H), 6.99 (d, J = 5.5 Hz, 146.70, 141.44, 1H),4.91 (dq, J = 9.2, 140.86, 137.46, 6.4 Hz, 1H), 4.57 (ddd, J = 10.9,128.87, 128.34, 8.5, 7.0 Hz, 1H), 125.88, 109.77, 83.70, 3.90 (s, 3H),3.56 (dd, J = 8.4, 6.3 Hz, 80.65, 75.29, 56.28, 1H), 3.34 (dd, J = 8.4,6.5 Hz, 51.51, 46.19, 36.73, 1H), 3.21-3.04 (m, 2H), 33.91, 29.28,26.57, 2.40 (s, 3H), 2.38-2.21 (m, 20.76, 19.56, 19.50, 2H), 1.96-1.78(m, 2H), 18.80, 18.16 1.61-1.51 (m, 2H), 1.50-1.38 (m, overlapping, 1H),1.44 (d, J = 6.4 Hz, 3H), 1.29-1.12 (m, 1H), 0.97 (dd, J = 6.7, 5.3 Hz,6H), 0.92-0.80 (m, 1H) F71 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 8.56 (d, J= 8.6 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.34 (d, J = 5.5 Hz,172.71, 168.90, 3379, ([M]⁺) 1H), 7.35-7.22 (m, 2H), 162.40, 159.77,2943, calcd for 7.00 (d, J = 5.5 Hz, 1H), 159.43, 146.72, 2868,C₃₀H₃₈N₂O₇, 6.99-6.89 (m, 3H), 5.07 (dq, J = 9.4, 141.42, 137.48, 1771,538.2679; 6.5 Hz, 1H), 4.61 (ddd, J = 10.9, 129.58, 120.93, 1737, found,8.3, 6.9 Hz, 1H), 115.56, 109.82, 1676, 538.2684 4.16 (t, J = 8.7 Hz,1H), 3.91 (s, 101.26, 101.07, 81.67, 1506, 3H), 2.40 (s, 3H), 74.88,56.30, 51.67, 1493, 1.92-1.32 (m, 15H), 1.28 (d, J = 6.3 Hz, 42.01,37.26, 36.85, 1172 3H), 1.20-1.06 (m, 1H), 33.66, 31.77, 27.65,1.07-0.88 (m, 2H) 25.04, 20.76, 19.07, 18.38 F72 — (Thin HRMS-ESI ¹H NMR(CDCl₃) δ — Film) (m/z) 8.53-8.43 (m, 1H), 8.32 (d, J = 5.5 Hz, 3378,([M]⁺) 1H), 7.15-7.03 (m, 2H), 2938, calcd for 6.99 (d, J = 5.5 Hz, 1H),1771, C₃₀H₃₈N₂O₈, 6.88-6.72 (m, 2H), 4.91 (dq, J = 9.3, 1742, 554.2628;6.4 Hz, 1H), 4.56 (dt, J = 10.9, 1678, found, 7.7 Hz, 1H), 3.90 (s, 3H),1510, 554.2644 3.79 (s, 3H), 3.57 (dd, J = 9.7, 1200 7.0 Hz, 1H), 3.44(dd, J = 9.7, 6.9 Hz, 1H), 3.15 (t, J = 9.1 Hz, 1H), 3.07 (d, J = 13.1Hz, 1H), 2.39 (s, 3H), 2.33-2.22 (m, 2H), 1.87-1.76 (m, 1H), 1.55-1.47(m, 2H), 1.49-1.38 (m, 1H), 1.45 (d, J = 6.5 Hz, 3H), 1.19-1.05 (m, 2H),0.91-0.80 (m, 1H), 0.64-0.47 (m, 2H), 0.32-0.20 (m, 2H) F73 — — ESIMS ¹HNMR (CDCl₃) δ 8.54 (s, ¹³C NMR (CDCl₃) δ m/z 517 1H), 8.34 (d, J = 5.4Hz, 1H), 172.71, 168.87, ([M + H]⁺) 7.00 (d, J = 5.5 Hz, 1H), 162.36,159.40, 4.94-4.82 (m, 1H), 4.55 (dt, J = 10.8, 146.71, 141.44, 7.5 Hz,1H), 3.90 (s, 3H), 137.44, 109.78, 3.49 (dd, J = 9.7, 7.0 Hz, 1H),101.25, 101.05, 84.33, 3.36 (dd, J = 9.7, 6.9 Hz, 1H), 78.50, 75.35,56.28, 2.99 (t, J = 8.9 Hz, 1H), 51.59, 42.29, 37.25, 2.39 (s, 3H),2.38-2.26 (m, 1H), 36.88, 33.94, 31.83, 1.92-1.66 (m, 4H), 25.09, 25.06,20.73, 1.64-1.44 (m, 10H), 1.40 (d, J = 6.5 Hz, 18.92, 18.06, 11.13,3H), 1.35-1.22 (m, 1H), 3.12, 2.93 1.15-0.91 (m, 3H), 0.60-0.50 (m, 2H),0.21 (dt, J = 6.0, 4.5 Hz, 2H) F74 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.55(d, J = 6.9 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.33 (d, J = 5.4 Hz,172.75, 168.89, ([M]⁺) 1H), 7.00 (d, J = 5.5 Hz, 162.36, 159.41, calcdfor 1H), 4.87 (dq, J = 9.3, 6.4 Hz, 146.70, 141.49, C₂₇H₄₀N₂O₇, 1H),4.55 (ddd, J = 10.8, 8.4, 137.46, 109.75, 84.56, 504.2836; 7.0 Hz, 1H),3.90 (s, 3H), 75.40, 75.35, 75.33, found, 3.63 (dt, J = 8.7, 6.4 Hz,1H), 56.28, 51.62, 42.21, 504.2858 3.43 (dt, J = 8.8, 6.8 Hz, 1H),37.27, 36.83, 33.94, 2.98 (t, J = 8.9 Hz, 1H), 2.40 (s, 31.79, 27.59,25.10, 3H), 2.33 (dt, J = 13.5, 7.1 Hz, 25.08, 23.54, 20.75, 1H),1.90-1.42 (m, 17H), 18.96, 18.08, 10.73 1.40 (d, J = 6.4 Hz, 3H),1.35-1.22 (m, 1H), 1.17-0.97 (m, 1H), 0.93 (t, J = 7.4 Hz, 3H) F75 — —HRMS-ESI ¹H NMR (CDCl₃) δ 8.55 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z)1H), 8.33 (d, J = 5.4 Hz, 172.76, 168.89, ([M]⁺) 1H), 7.00 (d, J = 5.4Hz, 162.36, 159.41, calcd for 1H), 4.87 (dq, J = 9.3, 6.4 Hz, 146.70,141.49, C₂₈H₄₂N₂O₇, 1H), 4.55 (ddd, J = 10.8, 8.4, 137.45, 109.75,84.28, 518.2992; 6.9 Hz, 1H), 3.90 (s, 3H), 80.39, 75.46, 56.28, found,3.46 (dd, J = 8.4, 6.1 Hz, 1H), 51.63, 42.23, 37.23, 518.2998 3.24 (dd,J = 8.4, 6.7 Hz, 1H), 36.73, 33.97, 31.73, 2.96 (t, J = 8.9 Hz, 1H),2.40 (s, 29.21, 27.58, 25.09, 3H), 2.36-2.26 (m, 1H), 20.75, 19.56,19.44, 1.92-1.42 (m, 13H), 1.40 (d, J = 6.4 Hz, 18.98, 18.14 3H),1.36-1.21 (m, 2H), 1.16-0.96 (m, 3H), 0.99-0.83 (m, 6H) F76 — — HRMS-ESI¹H NMR (CDCl₃) δ 8.57 (d, J = 7.3 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.34(d, J = 5.4 Hz, 172.74, 168.92, ([M]⁺) 1H), 7.34-7.23 (m, 2H), 162.39,159.67, calcd for 7.00 (d, J = 5.5 Hz, 1H), 159.42, 146.71, C₂₅H₃₀N₂O₇,6.95 (dd, J = 7.6, 5.2 Hz, 3H), 141.42, 137.48, 470.2053; 5.09 (dq, J =9.1, 6.4 Hz, 1H), 129.58, 120.98, found, 4.61 (ddd, J = 10.9, 8.2, 7.0Hz, 115.48, 109.80, 82.30, 470.2059 1H), 4.15 (t, J = 8.8 Hz, 1H),74.69, 56.29, 51.70, 3.91 (s, 3H), 2.40 (s, 3H), 37.61, 33.80, 32.47,2.36 (m, 1H), 1.99-1.86 (m, 1H), 20.76, 19.24, 18.27, 1.68 (ddt, J =17.7, 14.9, 8.9 Hz, 17.76 3H), 1.38 (m, 1H), 1.30 (d, J = 6.5 Hz, 3H),1.27 (m, 1H), 1.00 (d, J = 6.9 Hz, 3H) F77 68-70 — HRMS-ESI ¹H NMR(CDCl₃) δ 8.55 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.33 (d, J = 5.4 Hz,1H), 172.77, 168.94, [M + H]⁺ 7.42-7.24 (m, 5H), 7.00 (d, J = 5.5 Hz,162.39, 159.41, calcd for 1H), 4.94 (dq, J = 9.2, 146.72, 141.44,C₂₆H₃₃N₂O₇, 6.4 Hz, 1H), 4.71 (d, J = 10.8 Hz, 138.05, 137.46, 485.2282;1H), 4.63-4.54 (m, 128.47, 127.82, found, 2H), 3.90 (s, 3H), 3.22 (t, J= 8.9 Hz, 127.74, 109.78, 99.99, 485.2286 1H), 2.40 (s, 3H), 85.30,75.59, 75.19, 2.39-2.29 (m, 1H), 1.82-1.72 (m, 56.30, 51.63, 37.95, 1H),1.61 (ddt, J = 19.1, 9.4, 33.89, 32.32, 20.78, 5.7 Hz, 3H), 1.46 (d, J =6.4 Hz, 19.07, 18.20, 17.79 3H), 1.33 (q, J = 10.8 Hz, 1H), 1.16 (dd, J= 7.3, 3.7 Hz, 1H), 1.07 (d, J = 6.8 Hz, 3H) F78 — — HRMS-ESI ¹H NMR(CDCl₃) δ 8.57 (d, J = 7.3 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.34 (d, J =5.4 Hz, 172.65, 168.92, [M + H]⁺ 1H), 7.29 (d, J = 7.6 Hz, 162.39,159.45, calcd for 2H), 7.01 (d, J = 5.5 Hz, 1H), 146.72, 141.41,C₂₇H₃₅N₂O₈ 6.98-6.90 (m, 3H), 5.07 (dq, 129.62, 121.05, 515.2388, J =9.1, 6.5 Hz, 1H), 115.38, 109.80, 81.12, found 4.68-4.55 (m, 1H), 4.23(t, J = 8.8 Hz, 74.82, 70.80, 58.45, 515.2409 1H), 3.91 (s, 3H), 3.37(t, J = 6.8 Hz, 56.29, 51.63, 40.10, 2H), 3.26 (s, 3H), 33.81, 30.56,28.18, 2.44-2.34 (m, 4H), 20.76, 19.14, 18.33 1.86 (dddd, J = 23.6,19.2, 11.4, 6.0 Hz, 3H), 1.77-1.59 (m, 2H), 1.55-1.43 (m, 1H), 1.37 (d,J = 11.6 Hz, 1H), 1.28 (t, J = 6.0 Hz, 3H), 1.23-1.13 (m, 1H) F79 96-100 — ESIMS ¹H NMR (CDCl₃) δ 8.53 (d, J = 8.4 Hz, ¹³C NMR (CDCl₃) δm/z 561 1H), 8.33 (d, J = 5.5 Hz, 172.55, 168.83, ([M + H]⁺) 1H),7.35-7.27 (m, 2H), 162.34, 159.62, 7.10-6.94 (m, 8H), 5.12 (dq, 159.36,146.65, J = 9.1, 6.4 Hz, 1H), 4.63 (dt, J = 10.9, 141.31, 137.42, 7.5Hz, 1H), 4.33 (t, J = 8.9 Hz, 137.01, 135.34, 1H), 3.89 (s, 3H), 129.62,128.96, 2.97 (dd, J = 13.3, 3.2 Hz, 128.61, 121.12, 1H), 2.41 (s, 3H),115.50, 109.76, 81.10, 2.39-2.27 (m, 5H), 2.16-2.02 (m, 1H), 74.64,56.22, 51.52, 1.72-1.50 (m, 3H), 1.34 (d, J = 6.5 Hz, 45.62, 36.35,33.75, 3H), 1.33-1.19 (m, 26.67, 20.95, 20.69, 2H) 18.83, 18.31 F80 — —HRMS-ESI ¹H NMR (CDCl₃) δ 8.58 (d, J = 7.5 Hz, ¹³C NMR (CDCl₃) δ (m/z)1H), 8.33 (d, J = 5.4 Hz, 172.57, 168.89, [M + H]⁺ 1H), 7.39-7.22 (m,2H), 162.44, 159.44, calcd for 7.10-6.82 (m, 4H), 5.10 (dq, 159.18,146.77, C₂₆H₃₂O₇BrN₂, J = 9.1, 6.4 Hz, 1H), 141.32, 137.49, 563.1387;4.61 (ddd, J = 10.9, 8.1, 6.9 Hz, 129.75, 121.34, found, 1H), 4.22 (t, J= 8.7 Hz, 1H), 115.39, 109.91, 80.93, 563.1387 3.89 (s, 3H), 3.45 (ddd,J = 10.0, 74.67, 56.32, 51.66, 7.4, 5.0 Hz, 1H), 41.28, 34.17, 33.58,3.39-3.26 (m, 1H), 2.40 (s, 3H), 31.56, 28.28, 20.77, 2.43-2.33 (m, 1H),19.18, 18.27 2.19-1.98 (m, 2H), 1.88-1.75 (m, 2H), 1.75-1.57 (m, 2H),1.46-1.34 (m, 1H), 1.30 (d, J = 6.5 Hz, 3H), 1.26-1.15 (m, 1H) F81 — —HRMS-ESI ¹H NMR (CDCl₃) δ 8.58 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.34 (d,J = 5.4 Hz, 1H), 172.70, 168.92, [M + H]⁺ 7.29 (d, J = 7.9 Hz, 2H),162.39, 159.67, calcd for 7.00 (d, J = 5.5 Hz, 1H), 159.43, 146.71,C₂₆H₃₃O₇N₂, 6.99-6.90 (m, 3H), 5.18-5.00 (m, 141.44, 129.59, 485.2282;1H), 4.61 (dt, J = 10.6, 7.7 Hz, 120.94, 115.40, found, 1H), 4.20 (t, J= 8.8 Hz, 1H), 109.79, 81.46, 74.84, 485.2288 3.91 (s, 3H), 2.40 (s,3H), 56.29, 51.65, 44.96, 2.39-2.30 (m, 1H), 1.85 (dt, J = 14.6, 33.86,27.10, 23.53, 6.9 Hz, 1H), 20.76, 18.82, 18.36, 1.74-1.58 (m, 4H), 1.37(q, J = 11.5 Hz, 11.89 1H), 1.28 (d, J = 6.4 Hz, 3H), 1.26-1.19 (m, 1H),1.15 (d, J = 15.0 Hz, 1H), 0.87 (t, J = 7.2 Hz, 3H) F82 — — HRMS-ESI ¹HNMR (CDCl₃) δ 8.57 (d, J = 7.4 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.34 (d,J = 5.4 Hz, 172.57, 168.90, [M + H]⁺ 1H), 7.40-7.27 (m, 2H), 162.43,159.45, calcd for 7.10-6.86 (m, 4H), 158.92, 146.73, C₂₆H₃₁O₇N₂F₂,6.06-5.65 (m, 1H), 5.10 (dq, J = 9.1, 141.33, 137.51, 521.2094; 6.5 Hz,1H), 4.62 (ddd, J = 11.0, 129.84, 121.56, found, 8.3, 6.9 Hz, 1H), 4.22(t, 116.74 (t, J = 239.3 Hz), 521.2107 J = 8.7 Hz, 1H), 3.91 (s, 3H),115.26, 109.85, 80.59, 2.48-2.33 (m, 4H), 74.49, 56.30, 51.64, 2.14-1.94(m, 2H), 1.94-1.71 (m, 37.56, 35.79 (t, J = 20.9 Hz), 3H), 1.71-1.59 (m,1H), 33.55, 29.50, 1.47-1.34 (m, 1H), 1.30 (d, J = 6.5 Hz, 20.75, 19.30,18.24 3H), 1.29-1.22 (m, 1H) F83 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.55 (s,¹³C NMR (CDCl₃) δ (m/z) 1H), 8.33 (d, J = 5.4 Hz, 1H), 172.67, 168.92,[M + H]⁺ 7.00 (d, J = 5.4 Hz, 1H), 162.36, 159.40, calcd for 4.99-4.79(m, 1H), 4.56 (dt, J = 10.7, 146.70, 141.43, C₂₈H₄₁O₈N₂, 7.7 Hz, 1H),3.91 (s, 3H), 137.45, 109.76, 83.99, 533.2857; 3.55-3.38 (m, 4H), 3.25(dq, 78.39, 75.47, 75.33, found, J = 6.6, 3.3 Hz, 2H), 3.06 (t, J = 8.8Hz, 69.12, 56.28, 51.55, 533.2857 1H), 2.40 (s, 3H), 40.50, 33.86,30.65, 2.33 (dt, J = 13.3, 6.3 Hz, 1H), 28.19, 20.76, 18.96, 1.99 (d, J= 9.7 Hz, 1H), 18.06, 11.09, 10.66, 1.78-1.60 (m, 3H), 1.57-1.45 (m,3.18, 3.02, 2.95, 2.88 2H), 1.41 (d, J = 6.4 Hz, 3H), 1.30 (q, J = 11.8,11.4 Hz, 1H), 1.06 (ddd, J = 12.9, 11.1, 6.7 Hz, 3H), 0.60-0.48 (m, 4H),0.29-0.15 (m, 4H) F84 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 7.0 Hz,¹³C NMR (CDCl₃) δ (m/z) 1H), 8.20-7.97 (m, 172.64, 168.87, [M + H]⁺ 1H),7.06 (t, J = 7.9 Hz, 2H), 162.39, 159.42, calcd for 6.78 (d, J = 5.4 Hz,1H), 158.86, 146.73, C₃₀H₃₈O₈N₂, 6.76-6.64 (m, 3H), 4.71 (dq, J = 8.9,141.40, 137.46, 555.2701; 6.4 Hz, 1H), 4.36 (dt, J = 10.7, 129.42,120.60, found, 7.2 Hz, 1H), 3.80 (td, J = 7.1, 114.49, 109.82, 83.94,555.2713 6.3, 2.7 Hz, 2H), 3.68 (s, 78.22, 75.25, 66.18, 3H), 3.27 (dd,J = 9.6, 7.2 Hz, 56.29, 51.56, 40.29, 1H), 3.21 (dd, J = 9.6, 6.8 Hz,34.67, 33.81, 30.35, 1H), 2.91 (t, J = 8.9 Hz, 1H) 28.23, 20.75, 19.07,2.18 (s, 3H), 2.13 (dt, J = 13.2, 18.08, 11.09, 3.16, 6.8 Hz, 1H),2.06-1.90 (m, 2.93 1H), 1.71-1.55 (m, 2H), 1.48 (dddd, J = 25.6, 20.4,14.3, 7.2 Hz, 2H), 1.34 (dt, J = 22.3, 9.7 Hz, 1H), 1.22 (d, J = 6.4 Hz,3H), 1.18-1.02 (m, 1H), 0.86 (ddt, J = 12.2, 7.3, 4.1 Hz, 2H), 0.39-0.29(m, 2H), −0.01 (q, J = 4.8 Hz, 2H) F85 — — HRMS-ESI ¹H NMR (CDCl₃) δ8.63 (d, J = 6.9 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.32 (dd, J = 5.4,173.54, 168.83, [M + H]⁺ 1.5 Hz, 1H), 7.00 (d, J = 5.5 Hz, 162.26,159.39, calcd for 1H), 5.10-4.92 (m, 146.70, 141.43, C₂₀H₂₇O₇N₂, 1H),4.67-4.38 (m, 1H), 137.42, 109.81, 86.83, 407.1813; 3.89 (d, J = 1.5 Hz,3H), 73.26, 67.69, 56.27, found, 3.85-3.75 (m, 1H), 3.75-3.62 (m, 53.00,39.69, 36.09, 407.1829 1H), 3.42 (dd, J = 9.5, 6.3 Hz, 35.75, 32.56,21.77, 1H), 2.40 (d, J = 1.2 Hz, 3H), 20.73, 18.35 2.39-2.29 (m, 1H),2.13-1.93 (m, 2H), 1.89 (dd, J = 17.2, 7.8 Hz, 1H), 1.74 (td, J = 14.9,14.0, 5.0 Hz, 1H), 1.63 (t, J = 13.5 Hz, 1H), 1.57-1.44 (m, 1H), 1.41(d, J = 6.3 Hz, 3H), 1.36 (dd, J = 12.8, 6.0 Hz, 1H), 1.26 (s, 1H) F86 —— HRMS-ESI ¹H NMR (CDCl₃) δ 8.59 (s, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.35(d, J = 5.4 Hz, 1H), 172.71, 168.92, [M + H]⁺ 7.27 (d, J = 2.9 Hz, 2H),162.40, 159.43, calcd for 7.01 (d, J = 5.5 Hz, 1H), 6.93 (dd, J = 13.2,159.32, 146.72, C₂₆H₃₁N₂O₇, 7.6 Hz, 3H), 5.77 (ddd, 141.38, 138.52,483.2126; J = 18.2, 10.3, 8.1 Hz, 1H), 129.49, 121.09, found, 5.16 (dt,J = 9.1, 6.4 Hz, 1H), 116.17, 115.78, 483.2144 5.04 (d, J = 17.1 Hz,1H), 109.81, 80.51, 74.46, 4.95 (d, J = 10.3 Hz, 1H), 56.29, 51.68,47.45, 4.69-4.57 (m, 1H), 4.30 (t, J = 8.8 Hz, 33.80, 31.19, 20.76, 1H),3.91 (s, 3H), 19.75, 18.30 2.58-2.46 (m, 1H), 2.40 (s, 3H), 2.40-2.33(m, 1H), 1.89 (dq, J = 14.3, 7.4 Hz, 1H), 1.77 (td, J = 16.3, 15.5, 8.5Hz, 2H), 1.46-1.24 (m, 5H) F87 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.49 (d, J= 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.32 (dd, J = 5.4, 172.64,168.90, [M + H]⁺ 0.6 Hz, 1H), 162.38, 159.41, calcd for 7.33-7.26 (m,2H), 7.22-7.13 (m, 3H), 146.70, 141.43, C₂₇H₃₅N₂O₇, 6.99 (d, J = 5.5 Hz,1H), 140.75, 137.46, 499.2439; 4.90 (dq, J = 9.2, 6.4 Hz, 1H), 128.87,128.34, found, 4.57 (ddd, J = 10.9, 8.4, 7.0 Hz, 125.90, 109.78, 84.20,499.2449 1H), 3.89 (d, J = 0.9 Hz, 3H), 75.21, 69.22, 56.28, 3.82 (dq, J= 8.8, 6.9 Hz, 1H), 51.51, 45.94, 36.91, 3.63 (dq, J = 8.9, 7.0 Hz, 1H),33.90, 26.64, 20.76, 3.17 (t, J = 9.1 Hz, 1H), 18.75, 18.02, 15.73 3.09(dd, J = 13.2, 3.4 Hz, 1H), 2.39 (s, 3H), 2.35 (dd, J = 13.4, 11.8 Hz,1H), 2.32-2.20 (m, 1H), 1.83 (ddq, J = 12.2, 7.7, 3.7 Hz, 1H), 1.70-1.52(m, 2H), 1.50-1.38 (m, 1H), 1.45 (d, J = 6.4 Hz, 3H), 1.25 (t, J = 7.0Hz, 3H), 1.21-1.12 (m, 1H), 0.87 (ddt, J = 18.0, 6.4, 3.2 Hz, 1H) F88 —— HRMS-ESI ¹H NMR (CDCl₃) δ 8.49 (d, J = 8.4 Hz, ¹³C NMR (CDCl₃) δ (m/z)1H), 8.32 (d, J = 5.4 Hz, 172.63, 168.90, [M + H]⁺ 1H), 7.31-7.26 (m,1H), 162.38, 159.41, calcd for 7.22-7.14 (m, 3H), 6.99 (d, J = 5.4 Hz,146.70, 141.43, C₂₈H₃₇N₂O₇, 1H), 4.90 (dq, J = 9.2, 140.81, 137.46,513.2595; 6.4 Hz, 1H), 4.57 (ddd, J = 10.9, 128.87, 128.34, found, 8.4,7.0 Hz, 1H), 125.88, 109.77, 83.99, 513.2606 3.89 (s, 3H), 3.73 (dt, J =8.7, 6.5 Hz, 75.59, 75.25, 56.28, 1H), 3.59-3.41 (m, 1H), 51.51, 46.06,36.82, 3.16 (t, J = 9.1 Hz, 1H), 33.90, 26.61, 23.60, 3.10 (dd, J =13.3, 3.3 Hz, 1H), 20.76, 18.77, 18.09, 2.39 (s, 3H), 2.35 (dd, J =13.3, 10.75 11.8 Hz, 1H), 2.31-2.20 (m, 1H), 1.84 (ddt, J = 12.1, 8.2,3.9 Hz, 1H), 1.72-1.51 (m, 5H), 1.49-1.40 (m, 1H), 1.45 (d, J = 6.4 Hz,3H), 1.21-1.11 (m, 1H), 0.98 (t, J = 7.4 Hz, 3H), 0.91-0.79 (m, 1H) F8948-50 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.36 (d, J = 8.0 Hz, ¹³C NMR(CDCl₃) δ 3375, (m/z) 1H), 8.29 (d, J = 5.4 Hz, 172.82, 170.26, 2951,([M]⁺) 1H), 7.34-7.22 (m, 2H), 162.97, 160.25, 1746, calcd for 7.01-6.88(m, 4H), 5.75 (s, 159.71, 145.76, 1675, C₃₀H₄₀N₂O₈, 2H), 5.14-5.02 (m,1H), 143.94, 142.42, 1492, 556.2785; 4.62 (ddd, J = 10.8, 8.1, 7.0 Hz,129.57, 120.96, 1202 found, 1H), 4.26-4.17 (m, 1H), 115.49, 109.63,89.49, 556.2794 3.91 (s, 3H), 2.46-2.33 (m, 1H), 81.63, 74.87, 56.19,2.07 (s, 3H), 1.93-1.31 (m, 51.93, 43.23, 36.40, 7H), 1.30 (d, J = 6.4Hz, 3H), 33.62, 28.27, 27.88, 1.28-1.04 (m, 4H), 0.80 (d, J = 6.6 Hz,27.57, 23.04, 22.06, 3H), 0.79 (d, J = 6.6 Hz, 20.88, 18.94, 18.39 3H)F90 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR(CDCl₃) δ 3378, (m/z) 1H), 8.27 (d, J = 5.3 Hz, 172.86, 170.24, 2953,([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.92, 160.22, 1745, calcd for 1H),5.74 (s, 2H), 145.74, 143.88, 1678, C₂₈H₄₄N₂O₈, 4.94-4.80 (m, 1H), 4.57(ddd, J = 10.7, 142.48, 109.57, 89.49, 1506, 536.3098; 8.1, 7.0 Hz, 1H),3.91 (s, 3H), 84.30, 80.42, 75.43, 1203 found, 3.46 (dd, J = 8.4, 6.3Hz, 1H), 56.17, 51.86, 43.53, 536.3107 3.27 (dd, J = 8.4, 6.5 Hz, 1H),36.54, 33.67, 29.17, 3.07-2.95 (m, 1H), 28.09, 28.02, 27.55, 2.41-2.28(m, 1H), 2.07 (s, 3H), 22.96, 22.27, 20.85, 1.91-1.39 (m, 7H), 1.41 (d,J = 6.4 Hz, 19.50, 19.45, 18.84, 3H), 1.38-0.95 (m, 18.16 5H), 0.95-0.81(m, 12H) F91 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.32 (d, J = 8.1 Hz, ¹³CNMR (CDCl₃) δ 3378, (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.84, 170.27,2949, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.95, 160.23, 1742, calcd for1H), 5.74 (s, 2H), 145.76, 143.90, 1676, C₂₈H₄₂N₂O₈, 4.96-4.81 (m, 1H),4.63-4.50 (m, 1H), 142.50, 109.57, 89.52, 1504, 534.2941; 3.91 (s, 3H),3.57-3.31 (m 84.36, 78.65, 75.41, 1368, found, 2H), 3.09-2.97 (m, 1H),56.18, 51.85, 43.61, 1201 534.2945 2.43-2.25 (m, 1H), 2.07 (s, 3H),36.44, 33.71, 28.08, 1.85-1.45 (m, 6H), 1.42 (d, J = 6.4 Hz, 27.34,23.03, 22.22, 3H), 1.38-0.92 (m, 20.88, 18.74, 18.11, 6H), 0.89 (d, J =6.6 Hz, 3H), 11.13, 3.09, 3.02 0.88 (d, J = 6.6 Hz, 3H), 0.62-0.51 (m,2H), 0.27-0.17 (m, 2H) F92 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J= 8.1 Hz, ¹³C NMR (CDCl₃) δ 3378, (m/z) 1H), 8.28 (d, J = 5.4 Hz,172.87, 170.27, 2937, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.93, 160.24,1744, calcd for 1H), 5.74 (s, 2H), 145.74, 143.92, 1678, C₂₇H₄₂N₂O₈,4.93-4.81 (m, 1H), 4.57 (ddd, J = 10.8, 142.51, 109.56, 89.54, 1504,522.2941; 8.1, 7.0 Hz, 1H), 3.91 (s, 3H), 84.58, 75.42, 56.17, 1369,found, 3.69-3.58 (m, 1H), 51.86, 43.54, 36.51, 1202 522.2965 3.52-3.41(m, 1H), 3.08-2.98 (m, 33.71, 28.10, 27.48, 1H), 2.41-2.28 (m, 1H),23.54, 23.03, 22.22, 2.07 (s, 3H), 1.83-1.26 (m, 9H), 20.88, 18.81,18.11, 1.42 (d, J = 6.5 Hz, 3H), 10.71 1.26-0.95 (m, 4H), 0.94 (t, J =7.4 Hz, 3H), 0.89 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) F93 —(Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ3384, (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.82, 170.26, 2951, ([M]⁺) 1H),6.95 (d, J = 5.4 Hz, 162.95, 160.24, 1747, calcd for 1H), 5.74 (s, 2H),145.74, 143.92, 1678, C₂₈H₄₁F₃N₂O₈, 4.93-4.80 (m, 1H), 4.57 (ddd, J =10.8, 142.45, 127.16 (q, J = 276.1 Hz), 1506, 590.2815; 8.1, 7.0 Hz,1H), 3.91 (s, 3H), 109.59, 1371, found, 3.79-3.68 (m, 1H), 89.51, 84.84,75.03, 1252 590.2828 3.61-3.50 (m, 1H), 3.09-2.98 (m, 71.54, 56.17,51.85, 1H), 2.41-2.28 (m, 1H), 43.47, 36.47, 33.63, 2.28-2.12 (m, 2H),2.07 (s, 3H), 30.81 (q, J = 28.9 Hz), 1.91-1.29 (m, 9H), 1.40 (d, J =6.4 Hz, 28.19, 28.07, 27.46, 3H), 1.29-0.92 (m, 23.05 (q, J = 3.2 Hz),4H), 0.92-0.83 (m, 6H) 22.95, 22.16, 20.86, 18.83, 18.13 ¹⁹F NMR (CDCl₃)δ −66.44 F94 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.35 (d, J = 8.0 Hz, ¹³CNMR (CDCl₃) δ 3379, (m/z) 1H), 8.28 (d, J = 5.4 Hz, 173.03, 170.28,2952, ([M]⁺) 1H), 6.94 (d, J = 5.4 Hz, 162.92, 160.25, 1743, calcd for1H), 5.74 (s, 2H), 145.75, 143.93, 1678, C₂₉H₄₄N₂O₈, 4.90-4.78 (m, 1H),4.57 (ddd, J = 10.9, 142.54, 109.55, 89.57, 1505, 548.3098; 8.0, 6.6 Hz,1H), 83.55, 82.90, 75.85, 1369, found, 4.08-3.99 (m, 1H), 3.91 (s, 3H),3.14 (dd, 56.18, 52.12, 42.89, 1202 548.3112 J = 9.1, 7.9 Hz, 1H),36.86, 33.60, 32.75, 2.42-2.28 (m, 1H), 2.07 (s, 3H), 32.50, 28.27,23.04, 1.86-0.98 (m, 19H), 1.43 (d, 22.97, 22.96, 22.37, J = 6.5 Hz,3H), 0.89 (d, J = 6.6 Hz, 20.89, 19.19, 18.36 3H), 0.88 (d, J = 6.6 Hz,3H) F95 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.1 Hz, ¹³C NMR(CDCl₃) δ 3380, (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.82, 170.26, 2942,([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.94, 160.24, 1744, calcd for 1H),5.74 (s, 2H), 145.75, 143.92, 1678, C₂₅H₃₈N₂O₈, 4.92-4.78 (m, 1H), 4.58(ddd, J = 10.7, 142.50, 109.57, 89.53, 1504, 494.2628; 8.1, 7.1 Hz, 1H),3.91 (s, 3H), 86.42, 75.14, 61.21, 1369, found, 3.50 (s, 3H), 3.00-2.89(m, 56.18, 51.82, 43.57, 1202 494.2648 1H), 2.42-2.28 (m, 1H), 36.48,33.70, 28.25, 2.07 (s, 3H), 1.83-1.27 (m, 7H), 28.16, 27.25, 23.09, 1.43(d, J = 6.4 Hz, 3H), 22.18, 20.88, 18.75, 1.27-0.91 (m, 4H), 0.90 (d, J= 6.6 Hz, 18.06 3H), 0.88 (d, J = 6.6 Hz, 3H) F96 — (Neat) HRMS-ESI ¹HNMR (CDCl₃) δ 8.32 (d, J = 7.9 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H),8.28 (d, J = 5.4 Hz, 176.16, 172.86, 2953, ([M]⁺) 1H), 6.95 (d, J = 5.4Hz, 170.27, 162.92, 1735, calcd for 1H), 5.74 (s, 2H), 160.26, 145.70,1679, C₃₀H₄₄N₂O₉, 5.09-4.94 (m, 1H), 4.93-4.82 (m, 1H), 144.01, 142.39,1505, 576.3047; 4.68-4.54 (m, 1H), 3.91 (s, 109.60, 89.53, 76.13, 1368,found, 3H), 2.82-2.67 (m, 1H), 73.39, 56.18, 51.83, 1202 576.30602.45-2.31 (m, 1H), 2.07 (s, 3H), 44.09, 41.93, 36.34, 1.99-1.39 (m,13H), 33.51, 30.06, 29.98, 1.39-1.14 (m, 4H), 1.26 (d, J = 6.3 Hz,27.99, 27.90, 27.45, 3H), 1.14-0.96 (m, 2H), 25.70, 25.68, 22.89,0.92-0.77 (m, 6H) 22.19, 20.87, 18.74, 17.55 F97 — (Neat) HRMS-ESI ¹HNMR (CDCl₃) δ 8.32 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3380, (m/z) 1H),8.28 (d, J = 5.3 Hz, 172.84, 170.27, 2921, ([M]⁺) 1H), 6.94 (d, J = 5.4Hz, 162.94, 160.24, 1743, calcd for 1H), 5.74 (s, 2H), 145.76, 143.92,1677, C₃₀H₄₄N₂O₈, 4.96-4.81 (m, 1H), 4.57 (ddd, J = 10.8, 142.53,109.56, 89.54, 1504, 560.3098; 8.1, 7.0 Hz, 1H), 3.91 (s, 3H), 84.40,78.52, 75.41, 1314, found, 3.49 (dd, J = 9.6, 7.0 Hz, 1H), 56.18, 51.84,40.15, 1202 560.3097 3.37 (dd, J = 9.6, 6.8 Hz, 1H), 38.32, 35.07,34.60, 3.06-2.94 (m, 1H), 33.77, 32.35, 27.46, 2.43-2.27 (m, 1H), 2.07(s, 3H), 26.70, 26.50, 26.17, 1.80-1.42 (m, 11H), 1.41 (d, 20.89, 18.81,18.10, J = 6.4 Hz, 3H), 11.15, 3.17, 2.94 1.37-0.69 (m, 9H), 0.63-0.49(m, 2H), 0.28-0.16 (m, 2H) F98 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.29(d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3382, (m/z) 1H), 8.27 (d, J = 5.4 Hz,172.69, 170.23, 2939, ([M]⁺) 1H), 7.18-7.08 (m, 2H), 162.95, 161.27 (d,J = 243.6 Hz), 1746, calcd for 7.02-6.91 (m, 3H), 5.73 (s, 160.22, 1678,C₃₀H₃₇FN₂O₈, 2H), 4.99-4.85 (m, 1H), 145.75, 143.88, 1508, 572.2534;4.58 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.41, 136.32 (d, J = 3.2 Hz), 1314,found, 1H), 3.90 (s, 3H), 3.58 (dd, J = 9.7, 130.14 (d, J = 7.8 Hz),1203 572.2546 7.0 Hz, 1H), 3.45 (dd, J = 9.7, 115.11 (d, J = 21.0 Hz),6.8 Hz, 1H), 109.61, 3.21-3.14 (m, 1H), 3.14-3.05 (m, 1H), 89.46, 83.72,78.77, 2.40-2.25 (m, 2H), 2.06 (s, 75.18, 56.17, 51.75, 3H), 1.89-1.76(m, 1H), 46.16, 36.04, 33.62, 1.64-1.50 (m, 2H), 1.47-1.36 (m, 26.60,20.85, 18.76, 1H), 1.46 (d, J = 6.5 Hz, 3H), 18.08, 11.16, 3.14,1.31-1.06 (m, 2H), 3.00 0.96-0.81 (m, 1H), 0.64-0.52 (m, 2H), 0.32-0.19(m, 2H) F99 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J = 8.0 Hz, ¹³CNMR (CDCl₃) δ 3380, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.70, 170.24,2940, ([M]⁺) 1H), 7.36-7.26 (m, 2H), 162.97, 161.29 (d, J = 243.7 Hz),1751, calcd for 7.11-6.89 (m, 8H), 5.74 (s, 160.25, 1678, C₃₂H₃₅FN₂O₈,2H), 5.18-5.06 (m, 1H), 159.55, 145.75, 1508, 594.2377; 4.64 (ddd, J =11.0, 8.0, 6.9 Hz 143.95, 142.35, 1204 found, 1H), 4.39-4.28 (m, 1H),135.85 (d, J = 3.2 Hz), 594.2395 3.90 (s, 3H), 3.02-2.91 (m, 1H), 130.10(d, J = 7.8 Hz), 2.43-2.29 (m, 2H), 129.71, 121.25, 2.14-1.99 (m, 1H),2.07 (s, 3H), 115.46, 115.10 (d, J = 21.1 Hz), 1.74-1.62 (m, 2H),109.65, 1.62-1.46 (m, 1H), 1.34 (d, J = 6.4 Hz, 89.46, 80.98, 74.59,3H), 1.31-1.23 (m, 1H), 56.18, 51.84, 45.73, 1.10-0.98 (m, 1H) 36.10,33.55, 26.79, 20.85, 18.94, 18.34 F100 — (Neat) HRMS-ESI ¹H NMR (CDCl₃)δ 8.29 (d, J = 8.5 Hz, ¹³C NMR (CDCl₃) δ 3382, (m/z) 1H), 8.27 (d, J =5.4 Hz, 172.71, 170.26, 2938, ([M]⁺) 1H), 7.17-7.07 (m, 2H), 162.96,161.30 (d, J = 243.6 Hz), 1745, calcd for 7.02-6.90 (m, 3H), 160.24,1677, C₂₉H₃₅FN₂O₈, 6.03-5.88 (m, 1H), 5.74 (s, 2H), 145.75, 143.93,1507, 558.2377; 5.33 (dq, J = 17.2, 1.6 Hz, 142.43, 136.27 (d, J = 3.3Hz), 1202 found, 1H), 5.21 (dq, J = 10.4, 1.3 Hz, 134.31, 558.2390 1H),4.99-4.86 (m, 1H), 130.14 (d, J = 7.7 Hz), 4.59 (ddd, J = 10.9, 8.1, 7.0Hz, 117.14, 115.12 (d, J = 21.1 Hz), 1H), 4.29 (ddt, J = 12.2, 109.60,5.6, 1.4 Hz, 1H), 4.11 (ddt, J = 12.1, 89.50, 84.16, 75.04, 5.5, 1.4 Hz,1H), 3.90 (s, 74.70, 56.18, 51.77, 3H), 3.29-3.18 (m, 1H), 45.99, 36.11,33.63, 3.12-3.01 (m, 1H), 2.40-2.24 (m, 26.61, 20.88, 18.82, 2H), 2.07(s, 3H), 18.15 1.89-1.74 (m, 1H), 1.65-1.50 (m, 2H), ¹⁹F NMR (CDCl₃) δ−117.47 1.47 (d, J = 6.5 Hz, 3H), 1.47-1.34 (m, 1H), 1.28-1.14 (m, 1H),0.97-0.78 (m, 1H) F101 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.29 (d, J =8.1 Hz, ¹³C NMR (CDCl₃) δ 3381, (m/z) 1H), 8.26 (d, J = 5.4 Hz, 172.72,170.24, 2937, ([M]⁺) 1H), 7.17-7.07 (m, 2H), 162.95, 161.27 (d, J =243.5 Hz), 1745, calcd for 7.02-6.90 (m, 3H), 5.74 (s, 160.23, 1677,C₂₉H₃₇FN₂O₈, 2H), 4.98-4.84 (m, 1H), 145.75, 143.90, 1508, 560.2534;4.58 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.43, 136.40 (d, J = 3.1 Hz), 1372,found, 1H), 3.90 (s, 3H), 3.73 (dt, J = 8.6, 130.13 (d, J = 7.7 Hz),1203 560.2541 6.5 Hz, 1H), 3.52 (dt, J = 8.7, 115.09 (d, J = 21.1 Hz),6.7 Hz, 1H), 109.60, 3.21-3.11 (m, 1H), 3.11-3.01 (m, 1H), 89.49, 83.92,75.62, 2.41-2.25 (m, 2H), 2.06 (s, 75.19, 56.18, 51.77, 3H), 1.86-1.72(m, 1H), 46.17, 36.00, 33.64, 1.70-1.51 (m, 4H), 1.46 (d, J = 6.4 Hz,26.61, 23.58, 20.86, 3H), 1.46-1.35 (m, 1H), 18.81, 18.09, 10.731.30-1.13 (m, 1H), 0.98 (t, J = 7.4 Hz, ¹⁹F NMR (CDCl₃) δ −117.52 3H),0.94-0.79 (m, 1H) F102 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.29 (d, J =8.1 Hz, ¹³C NMR (CDCl₃) δ 3382, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.73,170.27, 2957, ([M]⁺) 1H), 7.18-7.05 (m, 2H), 162.95, 161.28 (d, J =243.5 Hz), 1744, calcd for 7.02-6.90 (m, 3H), 5.74 (s, 160.24, 1677,C₃₀H₃₉FN₂O₈, 2H), 4.98-4.83 (m, 1H), 145.75, 143.93, 1508, 574.2690;4.58 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.44, 136.44 (d, J = 3.2 Hz), 1369,found, 1H), 3.90 (s, 3H), 3.56 (dd, J = 8.4, 130.13 (d, J = 7.8 Hz),1203 574.2691 6.3 Hz, 1H), 3.33 (dd, J = 8.4, 115.11 (d, J = 21.0 Hz),6.5 Hz, 1H), 109.58, 3.19-3.10 (m, 1H), 3.10-3.01 (m, 1H), 89.52, 83.65,80.70, 2.41-2.24 (m, 2H), 2.07 (s, 75.24, 56.18, 51.77, 3H), 1.97-1.71(m, 2H), 46.31, 35.91, 33.66, 1.63-1.51 (m 2H), 1.45 (d, J = 6.4 Hz,29.27, 26.56, 20.88, 3H), 1.45-1.34 (m, 1H), 19.53, 19.49, 18.84,1.29-1.14 (m, 1H), 0.97 (d, J = 6.8 Hz, 18.16 3H), 0.96 (d, J = 6.8 Hz,¹⁹F NMR (CDCl₃) δ −117.53 3H), 0.93-0.79 (m, 1H) F103 — (Neat) HRMS-ESI¹H NMR (CDCl₃) δ 8.29 (d, J = 8.4 Hz, ¹³C NMR (CDCl₃) δ 3382, (m/z) 1H),8.27 (d, J = 5.4 Hz, 172.59, 170.25, 2940, ([M]⁺) 1H), 7.18-7.05 (m,2H), 162.98, 161.35 (d, J = 243.8 Hz), 1749, calcd for 7.03-6.89 (m,3H), 5.94 (tt, J = 55.2, 160.25, 1677, C₂₈H₃₃F₃N₂O₈, 3.9 Hz, 1H), 5.73(s, 145.76, 143.94, 1508, 582.2189; 2H), 5.02-4.84 (m, 1H), 142.34,135.86 (d, J = 3.2 Hz), 1203 found, 4.58 (ddd, J = 10.9, 8.1, 6.9 Hz,130.14 (d, J = 7.8 Hz), 582.2191 1H), 4.06-3.91 (m, 1H), 115.19 (d, J =21.1 Hz), 3.90 (s, 3H), 3.86-3.72 (m, 1H), 113.88 (t, J = 241.2 Hz),3.32-3.21 (m, 1H), 109.65, 3.11-2.98 (m, 1H), 2.44-2.24 (m, 89.47,85.53, 74.41, 2H), 2.06 (s, 3H), 72.60 (t, J = 27.6 Hz), 1.92-1.76 (m,1H), 1.68-1.38 (m, 3H), 56.19, 51.74, 45.81, 1.47 (d, J = 6.4 Hz, 3H),35.93, 33.51, 26.57, 1.30-1.15 (m, 1H), 0.98-0.80 (m, 20.86, 18.86,18.14 1H) ¹⁹F NMR (CDCl₃) δ −117.21 F104 — (Neat) HRMS-ESI ¹H NMR(CDCl₃) δ 8.29 (d, J = 7.8 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.27(d, J = 5.3 Hz, 176.11, 172.73, 2943, ([M]⁺) 1H), 7.12-7.02 (m, 2H),170.27, 162.94, 1732, calcd for 7.02-6.90 (m, 3H), 5.73 (s, 161.35 (d, J= 244.0 Hz), 1677, C₃₂H₃₉FN₂O₉, 2H), 5.11-4.94 (m, 2H), 160.26, 145.71,1507, 614.2640; found, 4.62 (ddd, J = 11.0, 8.0, 7.0 Hz, 144.01, 142.33,1201 614.2649 1H), 3.90 (s, 3H), 135.59 (d, J = 3.2 Hz), 2.80-2.69 (m,1H), 2.69-2.61 (m, 1H), 130.07 (d, J = 7.8 Hz), 2.42-2.29 (m, 2H), 2.07(s, 115.22 (d, J = 21.2 Hz), 3H), 2.01-1.43 (m, 11H), 109.63, 89.51,75.54, 1.36-1.16 (m, 2H), 1.29 (d, J = 5.6 Hz, 73.16, 56.18, 51.75, 3H),1.05-0.91 (m, 44.16, 44.01, 35.93, 1H) 33.44, 30.06, 30.04, 26.82,25.72, 25.70, 20.86, 18.73, 17.55 ¹⁹F NMR (CDCl₃) δ −117.11 F105 —(Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ3380, (m/z) 1H), 8.26 (d, J = 5.3 Hz, 176.42, 172.70, 2940, ([M]⁺) 1H),7.12-7.02 (m, 2H), 170.23, 162.94, 1734, calcd for 7.02-6.90 (m, 3H),5.73 (s, 161.34 (d, J = 244.1 Hz), 1677, C₃₀H₃₇FN₂O₉, 2H), 5.10-4.97 (m,2H), 160.25, 145.70, 1508, 588.2483; found, 4.62 (ddd, J = 10.9, 8.0,7.0 Hz, 143.98, 142.30, 1201 588.2484 1H), 3.91 (s, 3H), 2.65 (dd, J =14.0, 135.54 (d, J = 3.2 Hz), 3.6 Hz, 1H), 2.58 (hept, J = 7.0 Hz),130.05 (d, J = 7.7 Hz), 1H), 2.43-2.29 (m, 115.20 (d, J = 21.2 Hz), 2H),2.07 (s, 3H), 109.64, 89.46, 75.47, 2.00-1.85 (m, 1H), 1.77-1.44 (m,3H), 73.07, 56.17, 51.73, 1.35-1.17 (m, 1H), 1.29 (d, J = 5.8 Hz, 44.13,35.84, 34.19, 3H), 1.22 (d, J = 7.1 Hz, 33.40, 26.73, 20.84, 3H), 1.22(d, J = 6.9 Hz, 19.06, 18.97, 18.70, 3H); 1.06-0.91 (m, 1H) 17.48 ¹⁹FNMR (CDCl₃) δ −117.09 F106 — — ESIMS ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.3Hz, ¹³C NMR (CDCl₃) δ m/z 557.3 1H), 8.26 (d, J = 5.4 Hz, 172.76,170.27, ([M + H]⁺) 1H), 7.32-7.25 (m, 2H), 162.95, 160.23, 7.23-7.13 (m,3H), 6.94 (d, J = 5.4 Hz, 145.75, 143.90, 1H), 5.74 (s, 2H), 142.47,140.86, 4.91 (dq, J = 9.3, 6.5 Hz, 1H), 128.87, 128.34, 4.58 (ddd, J =10.9, 8.2, 7.0 Hz, 125.88, 109.58, 89.52, 1H), 3.90 (s, 3H), 83.71,80.66, 75.29. 3.57 (dd, J = 8.4, 6.2 Hz, 1H), 56.18, 51.79, 46.21, 3.34(dd, J = 8.4, 6.5 Hz, 1H), 36.74, 33.71, 29.28, 3.16 (t, J = 9.1 Hz,1H), 3.11 (dd, J = 13.3, 26.55, 20.88, 19.56, 3.2 Hz, 1H), 19.50, 18.84,18.18 2.41-2.26 (m, 2H), 2.06 (s, 3H), 1.97-1.77 (m, 2H), 1.58 (tt, J =8.6, 2.6 Hz, 2H), 1.46 (d, J = 6.4 Hz, 3H), 1.49-1.39 (m, 1H,overlapping), 1.27-1.13 (m, 1H), 0.97 (dd, J = 6.7, 5.4 Hz, 6H),0.91-0.83 (m, 1H) F107 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z555.4 8.36-8.20 (m, 2H), 7.33-7.23 (m, 172.73, 170.27, ([M + H]⁺) 2H),7.23-7.12 (m, 3H), 162.95, 160.23, 6.94 (d, J = 5.4 Hz, 1H), 5.73 (s,145.75, 143.89, 2H), 4.93 (dq, J = 9.1, 6.4 Hz, 142.45, 140.73, 1H),4.58 (ddd, J = 10.9, 8.1, 128.89, 128.35, 7.0 Hz, 1H), 3.90 (s, 3H),125.90, 109.58, 89.50, 3.59 (dd, J = 9.7, 7.0 Hz, 1H), 83.80, 78.76,75.24, 3.45 (dd, J = 9.7, 6.8 Hz, 1H), 56.18, 51.77, 46.07, 3.28-3.04(m, 2H), 2.42-2.23 (m, 36.89, 33.70, 26.58, 2H), 2.06 (s, 3H), 1.89(ddt, J = 12.2, 20.88, 18.76, 18.11, 8.3, 3.9 Hz, 1H), 11.18, 3.16, 3.011.66-1.50 (m, 2H), 1.49-1.38 (m, overlapping, 1H), 1.46 (d, J = 6.4 Hz,3H), 1.23-1.06 (m, 2H), 0.94-0.80 (m, 1H), 0.65-0.53 (m, 2H), 0.34-0.17(m, 2H) F108 — — ESIMS ¹H NMR (CDCl₃) δ 8.31 (d, J = 8.0 Hz, ¹³C NMR (75MHz, m/z 577.5 1H), 8.27 (d, J = 5.4 Hz, CDCl₃) δ 172.83, ([M + H]⁺)1H), 7.35-7.21 (m, 3H), 170.35, 163.08, 7.21-7.08 (m, 3H), 160.35,159.76, 7.06-6.91 (m, 4H), 5.74 (s, 2H), 145.85, 144.04, 5.12 (dq, J =9.1, 6.5 Hz, 1H), 142.52, 140.36, 4.63 (ddd, J = 10.9, 8.1, 7.0 Hz,129.81, 128.92, 1H), 4.36 (t, J = 8.9 Hz, 128.43, 126.07, 1H), 3.90 (s,3H), 3.02 (dd, J = 13.4, 121.32, 115.65, 3.3 Hz, 1H), 109.75, 89.59,81.26, 2.46-2.29 (m, 2H), 2.16-2.08 (m, 1H), 74.78, 56.28, 51.97, 2.06(s, 3H), 1.76-1.63 (m, 45.79, 37.01, 33.72, 2H), 1.63-1.49 (m, 1H),26.86, 20.97, 19.06, 1.35 (d, J = 6.5 Hz, 3H), 18.49 1.31-1.21 (m, 2H),1.09-0.96 (m, 1H) F109 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ(m/z) 8.34-8.24 (m, 2H), 7.34-7.24 (m, 172.78, 170.30, [M + H]⁺ 2H),7.24-7.13 (m, 3H), 162.97, 160.25, calcd for 6.94 (d, J = 5.4 Hz, 1H),5.73 (s, 145.77, 143.91, C₂₉H₃₉N₂O₈, 2H), 4.91 (dq, J = 9.2, 6.4 Hz,142.49, 140.82, 543.2701; 1H), 4.58 (ddd, J = 10.9, 8.1, 128.89, 128.35,found, 7.0 Hz, 1H), 3.90 (s, 3H), 125.89, 109.59, 89.51, 543.27073.78-3.70 (m, 1H), 3.57-3.48 (m, 84.00, 75.61, 75.26, 1H), 3.22-3.14 (m,1H), 56.18, 51.78, 46.08, 3.11 (dd, J = 13.2, 3.3 Hz, 1H), 36.82, 33.70,26.58, 2.41-2.24 (m, 2H), 2.06 (s, 23.60, 20.88, 18.80, 3H), 1.90-1.79(m, 1H), 18.11, 10.75. 1.73-1.53 (m, 4H), 1.50-1.38 (m, 1H), 1.46 (d, J= 6.4 Hz, 3H), 1.27-1.15 (m, 1H), 0.98 (t, J = 7.4 Hz, 3H), 0.94-0.81(m, 1H) F110 — — ESIMS ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.1 Hz, ¹³C NMR(CDCl₃) δ m/z 569.3 1H), 8.26 (d, J = 5.4 Hz, 172.95, 170.26, ([M + H]⁺)1H), 7.35-7.23 (m, 2H), 162.92, 160.23, 7.23-7.12 (m, 3H), 6.93 (d, J =5.4 Hz, 145.75, 143.91, 1H), 4.89 (dq, J = 9.1, 142.48, 141.13, 6.5 Hz,1H), 4.56 (ddd, J = 11.1, 128.89, 128.34, 8.1, 6.7 Hz, 1H), 125.82,109.57, 89.53, 4.13 (ddd, J = 9.5, 4.7, 2.7 Hz, 1H), 83.85, 82.36,75.69, 3.90 (s, 3H), 3.40-3.24 (m, 56.17, 52.01, 45.31, 1H), 3.20 (dd, J= 13.3, 3.3 Hz, 36.92, 33.53, 32.84, 1H), 2.36-2.19 (m, 2H), 32.56,29.70, 27.84, 2.06 (s, 3H), 1.89-1.67 (m, 23.03, 22.98, 20.87, 7H),1.64-1.53 (m, 4H), 19.13, 18.37 1.48 (d, J = 6.5 Hz, 3H), 1.45-1.36 (m,1H), 1.23-1.06 (m, 2H), 1.00-0.83 (m, 2H) F111 — — ESIMS ¹H NMR (CDCl₃)δ 8.27 (t, J = 7.0 Hz, ¹³C NMR (CDCl₃) δ m/z 529.3 2H), 7.24 (dt, J =39.0, 172.76, 170.27, ([M + H]⁺) 7.6 Hz, 5H), 6.94 (d, J = 5.4 Hz,162.95, 160.24, 1H), 5.73 (s, 2H), 145.76, 143.91, 4.91 (dq, J = 12.9,6.8 Hz, 1H), 142.47, 140.76, 4.58 (dt, J = 10.7, 7.6 Hz, 1H), 128.88,128.34, 3.90 (s, 3H), 3.82 (t, J = 7.8 Hz, 125.90, 109.58, 89.52, 1H),3.70-3.56 (m, 1H), 84.22, 75.21, 69.24, 3.19 (t, J = 9.0 Hz, 1H), 56.18,51.78, 45.97, 3.10 (dd, J = 13.1, 3.6 Hz, 1H), 36.92, 33.71, 26.61,2.53-2.23 (m, 2H), 2.06 (s, 20.88, 18.78, 18.04, 3H), 1.84 (qd, J = 8.0,3.7 Hz, 15.74 1H), 1.58 (dt, J = 9.6, 5.1 Hz, 2H), 1.47 (t, J = 5.8 Hz,4H), 1.25 (t, J = 6.3 Hz, 4H), 1.01-0.78 (m, 1H) F112 — — ESIMS ¹H NMR(CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 559.2 8.31-8.24 (m, 2H), 7.31-7.25 (m,172.70, 170.26, ([M + H]⁺) 2H), 7.23-7.14 (m, 3H), 162.94, 160.23, 6.93(d, J = 5.4 Hz, 1H), 5.73 (s, 145.75, 143.92, 2H), 4.94 (dq, J = 9.2,6.4 Hz, 142.46, 140.78, 1H), 4.58 (ddd, J = 10.9, 8.1, 128.91, 128.33,7.0 Hz, 1H), 3.95 (ddd, J = 9.9, 125.88, 109.57, 89.52, 6.0, 3.7 Hz,1H), 3.90 (s, 84.75, 75.06, 72.83, 3H), 3.72 (ddd, J = 10.4, 5.6, 72.16,59.09, 56.18, 3.4 Hz, 1H), 3.62-3.51 (m, 51.76, 45.85, 36.78, 2H), 3.40(s, 3H), 3.23 (t, J = 9.1 Hz, 33.70, 26.55, 20.88, 1H), 3.19-3.09 (m,18.81, 18.17 1H), 2.42-2.24 (m, 2H), 2.06 (s, 3H), 1.96-1.85 (m, 1H),1.63-1.53 (m, 2H), 1.48 (d, J = 6.4 Hz, 3H), 1.46-1.39 (m, 1H),1.25-1.15 (m, 1H), 0.93-0.81 (m, 1H) F113 — — ESIMS ¹H NMR (CDCl₃) δ8.33 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 563.6 1H), 8.28 (d, J = 5.4Hz, 172.86, 170.26, ([M + H]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.94, 160.24,1H), 5.74 (s, 2H), 4.87 (dq, J = 9.2, 145.74, 143.91, 6.4 Hz, 1H), 4.57(ddd, J = 10.8, 142.55, 109.56, 89.54, 8.2, 7.1 Hz, 1H), 84.33, 80.37,75.48, 3.91 (s, 3H), 3.46 (dd, J = 8.4, 6.1 Hz, 56.17, 51.87, 40.04,1H), 3.24 (dd, J = 8.4, 6.7 Hz, 38.15, 35.08, 34.60, 1H), 2.98 (t, J =8.8 Hz, 33.75, 32.27, 29.21, 1H), 2.42-2.27 (m, 1H), 27.47, 26.69,26.52, 2.07 (s, 3H), 1.83 (dt, J = 13.2, 6.6 Hz, 26.20, 20.87, 19.58,1H), 1.77-1.55 (m, 8H), 19.47, 18.87, 18.16 1.41 (d, J = 6.3 Hz, 3H),1.37-1.11 (m, 8H), 1.01-0.87 (m, 8H), 0.77 (t, J = 11.2 Hz, 1H) F114 — —HRMS-ESI ¹H NMR (CDCl₃) δ 8.31 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z)1H), 8.28 (d, J = 5.4 Hz, 172.75, 170.30, ([M]⁺) 1H), 7.36-7.23 (m, 2H),162.96, 160.25, calcd for 7.08-6.99 (m, 4H), 159.67, 157.83, C₃₃H₃₈N₂O₉,6.99-6.91 (m, 2H), 6.80 (d, J = 8.6 Hz, 145.74, 143.97, 606.2577; 2H),5.74 (s, 2H), 142.39, 132.22, found, 5.12 (dq, J = 9.2, 6.4 Hz, 1H),129.69, 121.18, 606.2585 4.63 (ddd, J = 10.9, 8.0, 6.8 Hz, 115.55,113.73, 1H), 4.33 (t, J = 8.9 Hz, 1H), 109.60, 89.52, 81.13, 3.91 (s,3H), 3.77 (s, 3H), 74.71, 56.19, 55.20, 3.00-2.90 (m, 1H), 2.42-2.25 (m,51.85, 45.83, 35.96, 2H), 2.07 (s, 3H), 33.65, 26.67, 20.89, 1.73-1.63(m, 2H), 1.63-1.50 (m, 2H), 18.91, 18.39 1.34 (d, J = 6.4 Hz, 3H),1.33-1.17 (m, 1H), 1.06-0.97 (m, 1H) F115 — — HRMS-ESI ¹H NMR (CDCl₃) δ8.35 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.29 (d, J = 5.4 Hz,172.84, 170.28, ([M]⁺) 1H), 7.35-7.25 (m, 2H), 162.97, 160.26, calcd for6.99-6.90 (m, 4H), 5.75 (s, 159.78, 145.75, C₃₁H₄₀N₂O₈, 2H), 5.07 (dq, J= 9.2, 6.5 Hz, 143.97, 142.46, 568.2785; 1H), 4.62 (ddd, J = 10.9, 8.0,129.58, 120.93, found, 6.9 Hz, 1H), 4.25-4.12 (m, 115.56, 109.61, 89.54,568.2786 1H), 3.91 (s, 3H), 2.41 (dtd, J = 13.7, 81.67, 74.89, 56.19,7.0, 1.4 Hz, 1H), 51.94, 42.05, 37.27, 2.07 (s, 3H), 1.92-1.76 (m, 3H),36.85, 33.71, 33.66, 1.76-1.59 (m, 4H), 31.77, 27.59, 25.04, 1.60-1.32(m, 7H), 1.30 (d, J = 6.5 Hz, 20.88, 19.10, 18.39. 3H), 1.20-1.06 (m,1H), 1.08-0.90 (m, 2H) F116 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR(CDCl₃) δ (m/z) 8.42-8.15 (m, 2H), 7.09 (d, J = 8.6 Hz, 172.74, 170.28,([M]⁺) 2H), 6.94 (d, J = 5.4 Hz, 162.94, 160.23, calcd for 1H), 6.83 (d,J = 8.6 Hz, 2H), 157.82, 145.75, C₃₁H₄₀N₂O₉, 5.73 (s, 2H), 4.92 (dq, J =9.1, 143.91, 142.46, 584.2734; 6.4 Hz, 1H), 4.58 (ddd, J = 10.9, 132.68,129.74, found, 8.1, 7.0 Hz, 1H), 3.90 (s, 113.77, 109.57, 89.52,584.2744 3H), 3.79 (s, 3H), 3.58 (dd, J = 9.7, 83.80, 78.77, 75.25, 7.0Hz, 1H), 3.45 (dd, J = 9.7, 56.18, 55.23, 51.76, 6.8 Hz, 1H), 3.17 (t, J= 9.0 Hz, 46.21, 35.92, 33.72, 1H), 3.08 (dd, J = 13.4, 26.52, 20.88,18.75, 3.4 Hz, 1H), 18.10, 11.18, 3.16, 2.41-2.22 (m, 2H), 2.06 (s, 3H),3.00 1.91-1.76 (m, 1H), 1.61-1.52 (m, 2H), 1.52-1.40 (m, 1H), 1.46 (d, J= 6.4 Hz, 3H), 1.23-1.17 (m, 1H), 1.17-1.07 (m, 1H), 0.91-0.77 (m, 1H),0.64-0.54 (m, 2H), 0.29-0.21 (m, 2H) F117 — — HRMS-ESI ¹H NMR (CDCl₃) δ8.33 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.3 Hz,172.85, 170.28, ([M]⁺) 1H), 6.94 (d, J = 5.4 Hz, 162.94, 160.24, calcdfor 1H), 5.74 (s, 2H), 4.89 (dq, J = 9.3, 145.75, 143.93, C₂₉H₄₂N₂O₈,6.4 Hz, 1H), 4.57 (dt, J = 10.8, 142.52, 109.55, 89.56, 546.2941; 7.3Hz, 1H), 3.91 (s, 3H), 84.35, 78.54, 75.38, found, 3.50 (dd, J = 9.6,7.0 Hz, 1H), 56.18, 51.87, 42.35, 546.2956 3.36 (dd, J = 9.6, 6.8 Hz,1H), 37.26, 36.89, 33.96, 3.01 (t, J = 8.9 Hz, 1H), 33.77, 31.84, 27.51,2.46-2.26 (m, 1H), 2.07 (s, 3H), 25.10, 25.07, 20.89, 1.91-1.43 (m,13H), 1.42 (d, 18.96, 18.10, 11.14, J = 6.5 Hz, 3H), 3.14, 2.941.36-1.26 (m, 1H), 1.18-0.92 (m, 4H), 0.60-0.49 (m, 2H), 0.21 (dt, J =6.0, 4.5 Hz, 2H) F118 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.28 (dd, J = 9.8,¹³C NMR (CDCl₃) δ (m/z) 6.7 Hz, 2H), 7.08 (d, J = 8.5 Hz, 172.78,170.28, ([M]⁺) 2H), 6.94 (d, J = 5.4 Hz, 162.96, 160.25, calcd for 1H),6.88-6.71 (m, 2H), 157.82, 145.75, C₃₁H₄₂N₂O₉, 5.74 (s, 2H), 4.96-4.73(m, 143.92, 142.49, 586.2890; 1H), 4.58 (ddd, J = 10.9, 8.1, 132.83,129.73, found, 7.0 Hz, 1H), 3.90 (s, 3H), 113.77, 109.59, 89.53,586.2905 3.79 (s, 3H), 3.56 (dd, J = 8.4, 6.2 Hz, 83.73, 80.65, 75.31,1H), 3.34 (dd, J = 8.4, 6.5 Hz, 56.18, 55.23, 51.81, 1H), 3.14 (t, J =9.0 Hz, 46.35, 35.79, 33.73, 1H), 3.07-2.99 (m, 1H), 31.60, 29.28,26.53, 2.41-2.20 (m, 2H), 2.06 (s, 3H), 22.67, 20.88, 19.56, 1.95-1.84(m, 1H), 19.50, 18.85, 18.18, 1.84-1.65 (m, 2H), 1.66-1.52 (m, 14.132H), 1.45 (d, J = 6.4 Hz, 3H), 1.32-1.21 (m, 1H), 1.00-0.93 (m, 6H),0.88-0.82 (m, 1H) F119 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.28 (dd, J = 8.8,¹³C NMR (CDCl₃) δ (m/z) 6.6 Hz, 2H), 7.08 (d, J = 8.5 Hz, 172.76,170.27, ([M]⁺) 2H), 6.94 (d, J = 5.4 Hz, 162.94, 160.23, calcd for 1H),6.83 (d, J = 8.6 Hz, 157.80, 145.74, C₃₀H₄₀N₂O₉, 2H), 5.74 (s, 2H), 4.90(dq, J = 9.2, 143.91, 142.47, 572.2734; 6.4 Hz, 1H), 4.58 (ddd, J =10.9, 132.77, 129.72, found, 8.1, 7.0 Hz, 1H), 113.75, 109.57, 89.52,572.2720 3.90 (s, 3H), 3.79 (s, 3H), 3.73 (dt, 84.00, 75.60, 75.26, J =8.7, 6.5 Hz, 1H), 3.52 (dt, J = 8.7, 56.18, 55.23, 51.78, 6.7 Hz, 1H),3.16 (t, J = 9.0 Hz, 46.21, 35.86, 33.73, 1H), 3.04 (dd, J = 13.4,26.54, 23.60, 20.88, 3.3 Hz, 1H), 18.79, 18.11, 10.75 2.43-2.22 (m, 2H),2.06 (s, 3H), 1.79 (ddq, J = 12.2, 7.4, 3.7 Hz, 1H), 1.70-1.52 (m, 5H),1.45 (d, J = 6.4 Hz, 3H), 1.25-1.13 (m, 1H), 0.98 (t, J = 7.4 Hz, 3H),0.93-0.81 (m, 1H) F120 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 8.31 (d, J =8.1 Hz, ¹³C NMR (CDCl₃) δ Film) (m/z) 1H), 8.27 (d, J = 5.3 Hz, 172.78,170.29, 3379, ([M]⁺) 1H), 7.30 (dd, J = 1.9, 0.9 Hz, 162.93, 160.24,2954, calcd for 1H), 6.94 (d, J = 5.4 Hz, 154.69, 145.75, 1744,C₂₈H₃₈N₂O₉, 1H), 6.28 (dd, J = 3.1, 1.9 Hz, 143.93, 142.45, 1677,546.2577; 1H), 6.02 (d, J = 3.1 Hz, 1H), 141.01, 110.09, 1505, found,5.74 (s, 2H), 4.92 (dq, J = 9.2, 109.56, 106.04, 89.54, 1202 546.26026.4 Hz, 1H), 4.58 (ddd, J = 10.8, 83.46, 80.26, 75.19, 8.0, 6.8 Hz, 1H),3.90 (s, 56.18, 51.80, 43.22, 3H), 3.50 (dd, J = 8.4, 6.5 Hz, 33.63,29.34, 29.20, 1H), 3.30 (dd, J = 8.4, 6.4 Hz, 27.89, 20.89, 19.49, 1H),3.14 (t, J = 9.0 Hz, 1H), 19.46, 18.85, 18.17 3.01 (dd, J = 14.7, 3.5Hz, 1H), 2.52 (dd, J = 14.6, 11.2 Hz, 1H), 2.31 (dt, J = 12.6, 6.4 Hz,1H), 2.07 (s, 3H), 2.01-1.91 (m, 1H), 1.87 (dt, J = 13.2, 6.6 Hz, 1H),1.55 (dddd, J = 20.1, 12.2, 10.0, 5.2 Hz, 3H), 1.44 (d, J = 6.4 Hz, 3H),1.36-1.20 (m, 1H), 1.06-0.95 (m, 1H), 0.94 (d, J = 6.7 Hz, 6H) F121 — —HRMS-ESI ¹H NMR (CDCl₃) δ 8.32 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z)1H), 8.28 (d, J = 5.3 Hz, 176.47, 172.86, ([M]⁺) 1H), 6.95 (d, J = 5.4Hz, 170.29, 162.93, calcd for 1H), 5.74 (d, J = 0.8 Hz, 2H), 160.27,145.71, C₂₉H₄₂N₂O₉, 5.00 (dq, J = 9.4, 6.3 Hz, 1H), 144.03, 142.42,562.2890; 4.85 (t, J = 9.1 Hz, 1H), 109.59, 89.56, 76.08, found, 4.61(ddd, J = 10.9, 7.9, 6.9 Hz, 73.32, 56.18, 51.84, 562.2888 1H), 3.91 (s,3H), 2.57 (hept, J = 7.0 Hz, 40.64, 37.00, 36.53, 1H), 2.39 (dtd, J =13.2, 34.29, 33.68, 33.57, 6.5, 1.9 Hz, 1H), 2.07 (s, 31.86, 27.31,25.03, 3H), 1.91-1.27 (m, 13H), 25.02, 20.87, 19.11, 1.25 (d, J = 6.3Hz, 3H), 18.95, 18.86, 17.50 1.19 (dd, J = 7.0, 1.6 Hz, 6H), 1.13-1.00(m, 3H), 1.00-0.86 (m, 1H) F122 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.33 (d, J= 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.85,170.24, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.93, 160.23, calcd for 1H),5.74 (s, 2H), 4.87 (dq, J = 9.2, 145.74, 143.89, C₂₈H₄₂N₂O₈, 6.4 Hz,1H), 4.57 (ddd, J = 10.8, 142.50, 109.58, 89.50, 534.2941; 8.1, 6.9 Hz,1H), 84.55, 75.37, 75.32, found, 3.91 (s, 3H), 3.64 (dt, J = 8.7, 6.4Hz, 56.17, 51.87, 42.22, 534.2945 1H), 3.44 (dt, J = 8.7, 6.7 Hz, 37.25,36.81, 33.92, 1H), 3.00 (t, J = 8.8 Hz, 33.72, 31.77, 27.54, 1H),2.41-2.29 (m, 1H), 25.08, 25.06, 23.53, 2.07 (s, 3H), 1.94-1.39 (m,15H), 20.86, 18.98, 18.08, 1.41 (d, J = 6.3 Hz, 3H), 10.72 1.37-1.22 (m,1H), 1.17-0.98 (m, 3H), 0.94 (t, J = 7.4 Hz, 3H) F123 — — HRMS-ESI ¹HNMR (CDCl₃) δ 8.33 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d,J = 5.4 Hz, 172.86, 170.25, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.93,160.23, calcd for 1H), 5.74 (s, 2H), 4.87 (dq, J = 9.2, 145.74, 143.90,C₂₉H₄₄N₂O₈, 6.4 Hz, 1H), 4.57 (ddd, J = 10.8, 142.52, 109.57, 89.53,548.3098; 8.1, 6.9 Hz, 1H), 84.28, 80.39, 75.44, found, 3.91 (s, 3H),3.47 (dd, J = 8.4, 6.1 Hz, 56.17, 51.89, 42.25, 548.3094 1H), 3.24 (dd,J = 8.4, 6.7 Hz, 37.22, 36.72, 33.96, 1H), 2.98 (t, J = 8.8 Hz, 33.74,31.72, 29.20, 1H), 2.41-2.29 (m, 1H), 27.54, 25.09, 25.07, 2.07 (s, 3H),1.90-1.38 (m, 11H), 20.87, 19.55, 19.44, 1.41 (d, J = 6.5 Hz, 3H),19.01, 18.15 1.37-1.21 (m, 2H), 1.17-0.96 (m, 5H), 0.92 (t, J = 6.8 Hz,6H) F124 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.36 (d, J = 8.0 Hz, ¹³C NMR(CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.85, 170.29, ([M]⁺) 1H),7.34-7.24 (m, 2H), 162.96, 160.26, calcd for 7.01-6.88 (m, 4H), 5.75 (s,159.68, 145.75, C₂₆H₃₂N₂O₈, 2H), 5.09 (dq, J = 9.1, 6.4 Hz, 143.97,142.41, 500.2159; 1H), 4.63 (dt, J = 10.9, 7.1 Hz, 129.59, 120.98,found, 1H), 4.17 (t, J = 8.8 Hz, 1H), 115.48, 109.60, 89.54, 500.21623.91 (s, 3H), 2.41 (dt, J = 13.0, 82.29, 74.69, 56.19, 6.6 Hz, 1H), 2.07(s, 3H), 51.95, 37.67, 33.62, 1.93 (dd, J = 9.2, 5.4 Hz, 1H), 32.38,20.89, 19.26, 1.80-1.61 (m, 3H), 1.40 (dt, J = 13.5, 18.30, 17.76 10.7Hz, 1H), 1.31 (d, J = 6.4 Hz, 3H), 1.29-1.24 (m, 1H), 1.01 (d, J = 6.9Hz, 3H) F125 142-147 — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.0 Hz,¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.89, 170.32, [M +H]⁺ 1H), 7.40-7.28 (m, 5H), 162.96, 160.25, calcd for 6.95 (d, J = 5.4Hz, 1H), 145.77, 143.94, C₂₇H₃₅N₂O₈, 5.75 (s, 2H), 4.95 (dq, J = 9.2,6.4 Hz, 142.47, 138.05, 515.2388; 1H), 4.72 (d, J = 10.8 Hz, 128.47,127.82, found, 1H), 4.64-4.55 (m, 2H), 127.75, 109.58, 89.56, 515.23903.91 (s, 3H), 3.23 (t, J = 8.9 Hz, 85.30, 75.60, 75.20, 1H), 2.37 (dt, J= 13.3, 6.7 Hz, 56.19, 51.89, 37.99, 1H), 2.07 (s, 3H), 33.71, 32.27,20.90, 1.82-1.72 (m, 1H), 1.70-1.58 (m, 3H), 19.10, 18.22, 17.79 1.48(d, J = 6.4 Hz, 3H), 1.41-1.30 (m, 1H), 1.18 (dt, J = 7.5, 3.5 Hz, 1H),1.08 (d, J = 6.8 Hz, 3H) F126 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃)δ m/z 571 8.25-8.16 (m, 2H), 7.06-6.94 (m, 171.71, 169.22, ([M + H]⁺)4H), 6.86 (d, J = 5.4 Hz, 1H), 161.90, 159.19, 5.66 (s, 2H), 4.83 (dq, J= 9.3, 144.70, 142.86, 6.4 Hz, 1H), 4.50 (dt, J = 11.0, 141.42, 136.64,7.5 Hz, 1H), 3.82 (s, 3H), 134.27, 127.98, 3.49 (dd, J = 8.4, 6.2 Hz,1H), 127.68, 108.54, 88.47, 3.26 (dd, J = 8.4, 6.5 Hz, 1H), 82.67,79.59, 74.25, 3.07 (t, J = 9.0 Hz, 1H), 2.99 (dd, J = 13.2, 55.13,50.74, 45.17, 3.1 Hz, 1H), 2.24 (s, 35.19, 32.67, 28.22, 5H), 1.99 (s,3H), 25.46, 19.97, 19.83, 1.90-1.69 (m, 2H), 1.59-1.45 (m, 2H), 18.51,18.45, 17.77, 1.44-1.30 (m, 4H), 17.13 1.17-1.05 (m, 1H), 0.92-0.86 (m,6H), 0.83-0.73 (m, 1H) F127 55-60 — ESIMS ¹H NMR (CDCl₃) δ 8.28 (d, J =8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 569 1H), 8.26 (d, J = 5.4 Hz, 172.65,170.17, ([M + H]⁺) 1H), 7.12-7.04 (m, 4H), 162.86, 160.14, 6.94 (d, J =5.4 Hz, 1H), 145.67, 143.80, 5.73 (s, 1H), 4.92 (dq, J = 9.2, 6.4 Hz,142.35, 137.47, 1H), 4.58 (ddd, J = 10.9, 135.25, 128.95, 8.2, 7.0 Hz,1H), 3.90 (s, 3H), 128.66, 109.51, 89.40, 3.59 (dd, J = 9.7, 7.0 Hz,1H), 83.70, 78.66, 75.16, 3.45 (dd, J = 9.7, 6.9 Hz, 1H), 56.10, 51.68,46.01, 3.17 (t, J = 9.1 Hz, 1H), 36.30, 33.61, 26.44, 3.10 (dd, J =13.3, 3.3 Hz, 1H), 20.93, 20.79, 18.65, 2.40-2.23 (m, 5H), 2.06 (s,18.02, 11.09, 3.07, 3H), 1.94-1.79 (m, 1H), 2.92 1.65-1.39 (m, 5H),1.33-1.08 (m, 3H), 0.92-0.82 (m, 2H), 0.65-0.54 (m, 2H), 0.25 (dtd, J =5.5, 3.9, 3.5, 1.6 Hz, 2H) F128 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J= 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 170.35,167.84, ([M + Na]⁺) 1H), 6.95 (d, J = 5.4 Hz, 160.52, 157.81, calcd for1H), 5.74 (s, 2H), 4.90 (dq, J = 9.1, 143.31, 141.51, C₂₅H₃₇FN₂O₈Na, 6.4Hz, 1H), 4.58 (ddt, J = 9.4, 140.02, 107.14, 87.11, 535.2426; 5.9, 4.6Hz, 2H), 81.42, 81.36, 79.73, found, 4.50-4.39 (m, 1H), 3.91 (s, 3H),77.78, 72.81, 53.74, 535.2423 3.45 (dd, J = 8.4, 6.6 Hz, 1H), 49.43,37.34, 37.30, 3.26 (dd, J = 8.4, 6.4 Hz, 1H), 31.13, 29.17, 28.98,3.14-3.02 (m, 1H), 2.36 (dt, J = 12.9, 26.73, 26.26, 18.44, 6.7 Hz, 1H),2.07 (s, 17.02, 16.98, 16.74, 3H), 2.06-1.98 (m, 1H), 15.69 1.84 (dp, J= 13.4, 6.7 Hz, 1H), 1.78-1.60 (m, 4H), 1.57 (s, 1H), 1.42 (d, J = 6.4Hz, 3H), 1.39-1.29 (m, 1H), 1.10 (dd, J = 14.3, 5.7 Hz, 1H), 0.92 (d, J= 6.8 Hz, 6H) F129 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.36 (d, J = 8.0 Hz,¹³C NMR (CDCl₃) δ (m/z) 1H), 8.29 (d, J = 5.4 Hz, 171.99, 169.51, ([M +H]⁺) 1H), 7.33-7.27 (m, 2H), 162.20, 159.49, calcd for 7.25-7.21 (m,2H), 158.57, 158.01, C₃₃H₃₉N₂O₉, 7.02-6.87 (m, 5H), 6.86-6.77 (m,144.98, 143.21, 607.2650; 2H), 5.75 (s, 2H), 141.63, 128.91, found,5.19-5.04 (m, 1H), 4.64 (dt, J = 10.9, 7.0 Hz, 128.61, 120.40, 607.26641H), 4.29 (t, J = 8.7 Hz, 119.82, 114.64, 1H), 3.96 (t, J = 6.0 Hz, 2H),113.68, 108.83, 88.76, 3.91 (s, 3H), 2.41 (dt, J = 12.6, 80.39, 74.00,65.27, 6.4 Hz, 1H), 2.07 (s, 5H), 55.41, 51.14, 39.45, 1.98-1.84 (m,1H), 1.84-1.64 (m, 32.81, 29.76, 27.68, 3H), 1.40 (q, J = 11.3 Hz, 1H),20.11, 18.54, 17.56 1.32 (d, J = 6.5 Hz, 3H), 1.29-1.20 (m, 1H) F130 — —HRMS-ESI ¹H NMR (CDCl₃) δ 8.36 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z)1H), 8.29 (d, J = 5.4 Hz, 172.77, 170.29, ([M + H]⁺) 1H), 7.33-7.27 (m,2H), 162.97, 160.26, calcd for 6.98-6.91 (m, 4H), 5.75 (s, 159.47,145.75, C₂₈H₃₇N₂O₉, 2H), 5.08 (dq, J = 9.1, 6.5 Hz, 143.99, 142.43,545.2494; 1H), 4.63 (dt, J = 10.9, 7.0 Hz, 129.62, 121.06, found, 1H),4.25 (t, J = 8.8 Hz, 1H), 115.39, 109.61, 89.54, 545.2519 3.91 (s, 3H),3.38 (t, J = 6.8 Hz, 81.12, 74.83, 70.80, 2H), 3.26 (s, 3H), 2.41 (dt,58.44, 56.19, 51.90, J = 12.4, 6.3 Hz, 1H), 2.07 (s, 40.15, 33.63,30.56, 3H), 1.99-1.78 (m, 3H), 28.14, 20.89, 19.18, 1.78-1.61 (m, 2H),1.49 (ddt, J = 13.6, 18.35 10.1, 6.6 Hz, 1H), 1.44-1.33 (m, 1H), 1.30(d, J = 6.5 Hz, 3H), 1.23-1.14 (m, 1H) F131 — — HRMS-ESI ¹H NMR (CDCl₃)δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz,172.79, 170.28, [M + H]⁺ 1H), 6.94 (d, J = 5.4 Hz, 162.95, 160.25, calcdfor 1H), 5.74 (s, 2H), 145.75, 143.95, C₂₆H₄₁N₂O₈S, 4.96-4.83 (m, 1H),4.58 (dt, J = 10.8, 7.0 Hz, 142.48, 109.57, 89.55, 541.2578; 1H), 3.91(s, 3H), 83.95, 80.40, 75.34, found, 3.45 (dd, J = 8.4, 6.5 Hz, 1H),56.18, 51.86, 42.31, 541.2581 3.27 (dd, J = 8.4, 6.5 Hz, 1H), 33.59,32.17, 29.99, 3.04 (t, J = 8.7 Hz, 1H), 2.59 (ddd, 29.20, 27.81, 20.89,J = 12.8, 9.7, 4.6 Hz, 1H), 19.49, 18.99, 18.14, 2.49-2.41 (m, 1H),2.41-2.31 (m, 15.39 1H), 2.10 (s, 3H), 2.07 (s, 3H), 1.94 (ddd, J =11.9, 9.5, 6.9 Hz, 1H), 1.84 (dt, J = 13.2, 6.6 Hz, 1H), 1.80-1.60 (m,3H), 1.52 (ddt, J = 13.9, 9.7, 4.7 Hz, 2H), 1.41 (d, J = 6.4 Hz, 3H),1.34 (q, J = 11.1 Hz, 1H), 1.09-1.00 (m, 1H), 0.92 (dd, J = 6.7, 1.0 Hz,6H) F132 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.0 Hz, ¹³C NMR(CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.82, 170.27, [M + Na]⁺ 1H),6.95 (d, J = 5.4 Hz, 162.94, 160.25, calcd for 1H), 5.74 (s, 2H), 4.88(dq, J = 9.1, 145.74, 143.94, C₂₆H₄₀O₉N₂Na, 6.4 Hz, 1H), 4.58 (dt, J =10.8, 142.50, 109.57, 89.55, 547.2626; 7.3 Hz, 1H), 3.91 (s, 3H), 84.05,80.35, 75.38, found, 3.42 (q, J = 7.6, 6.9 Hz, 3H), 71.28, 58.49, 56.18,547.2652 3.32 (s, 3H), 3.32-3.26 (m, 51.88, 40.27, 33.65, 1H), 3.05 (t,J = 8.8 Hz, 1H), 30.41, 29.17, 28.37, 2.36 (dt, J = 13.2, 6.5 Hz, 1H),20.88, 19.51, 19.43, 2.07 (s, 3H), 2.02-1.91 (m, 19.11, 18.15 1H), 1.84(dq, J = 13.2, 6.6 Hz, 1H), 1.67 (tq, J = 20.9, 8.5, 6.2 Hz, 3H),1.59-1.44 (m, 2H), 1.41 (d, J = 6.4 Hz, 3H), 1.33 (q, J = 11.2 Hz, 1H),1.10-0.99 (m, 1H), 0.92 (dd, J = 6.7, 2.6 Hz, 6H) F133 — — HRMS-ESI ¹HNMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d,J = 5.4 Hz, 172.88, 170.27, [M + H]⁺ 1H), 6.95 (d, J = 5.4 Hz, 162.94,160.24, calcd for 1H), 5.74 (s, 2H), 4.88 (dq, J = 9.2, 145.75, 143.93,C₂₅H₃₉O₈N₂, 6.4 Hz, 1H), 142.53, 109.56, 89.56, 495.2701; 4.68-4.49 (m,1H), 3.91 (s, 3H), 3.43 (dd, 84.25, 80.41, 75.44, found, J = 8.4, 6.6Hz, 1H), 3.27 (dd, 56.17, 51.88, 45.22, 495.2717 J = 8.4, 6.4 Hz, 1H),3.01 (t, J = 8.9 Hz, 33.74, 29.18, 27.13, 1H), 2.35 (dt, J = 12.8,23.27, 20.88, 19.49, 6.9 Hz, 1H), 2.07 (s, 3H), 19.45, 18.81, 18.18,1.83 (dd, J = 13.2, 6.6 Hz, 11.96 1H), 1.80-1.69 (m, 2H), 1.65-1.47 (m,2H), 1.41 (d, J = 6.4 Hz, 4H), 1.38-1.27 (m, 1H), 1.22 (ddd, J = 13.2,10.8, 7.3 Hz, 1H), 1.05-0.95 (m, 1H), 0.91 (d, J = 6.8 Hz, 9H) F13471-75 — ESIMS ¹H NMR (CDCl₃) δ 8.32 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δm/z 591 1H), 8.27 (d, J = 5.4 Hz, 172.65, 170.18, ([M + H]⁺) 1H),7.34-7.28 (m, 2H), 162.89, 160.16, 7.09-6.95 (m, 7H), 6.94 (d, J = 5.4Hz, 159.61, 145.67, 1H), 5.74 (s, 2H), 143.86, 142.30, 5.12 (dq, J =9.2, 6.4 Hz, 1H), 137.00, 135.31, 4.63 (ddd, J = 11.0, 8.1, 7.0 Hz,129.60, 128.94, 1H), 4.34 (t, J = 8.9 Hz, 128.60, 121.10, 1H), 3.89 (s,3H), 2.97 (dd, J = 13.4, 115.48, 109.55, 89.40, 3.2 Hz, 1H), 81.08,74.61, 56.10, 2.43-2.27 (m, 5H), 2.15-2.02 (m, 4H), 51.77, 45.65, 36.33,1.77-1.48 (m, 2H), 1.35 (d, J = 6.5 Hz, 33.54, 26.58, 20.93, 3H),1.32-1.19 (m, 20.79, 18.31, 14.05 2H) F135 — — HRMS-ESI ¹H NMR (CDCl₃) δ8.38 (d, J = 7.9 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz,172.69, 170.27, [M + H]⁺ 1H), 7.30 (dd, J = 8.6, 7.4 Hz, 162.99, 160.26,calcd for 2H), 7.07-6.87 (m, 4H), 159.18, 145.79, C₂₇H₃₄O₈BrN₂, 5.74 (s,2H), 5.11 (dq, J = 9.1, 143.95, 142.33, 593.1493; 6.5 Hz, 1H), 4.63 (dt,J = 10.9, 129.75, 121.33, found, 6.9 Hz, 1H), 4.24 (t, J = 8.7 Hz,115.38, 109.69, 89.48, 593.1499 1H), 3.91 (s, 3H), 80.92, 74.65, 56.22,3.46 (ddd, J = 10.0, 7.3, 5.0 Hz, 51.92, 41.32, 34.14, 1H), 3.41-3.28(m, 1H), 33.39, 31.57, 28.20, 2.50-2.36 (m, 1H), 2.20-1.99 (m, 20.89,19.20, 18.28 5H), 1.93-1.75 (m, 2H), 1.70 (dt, J = 16.7, 7.1 Hz, 2H),1.51-1.36 (m, 1H), 1.31 (d, J = 6.5 Hz, 3H), 1.27-1.15 (m, 1H) F136 — —HRMS-ESI ¹H NMR (CDCl₃) δ 8.36 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z)1H), 8.29 (d, J = 5.4 Hz, 172.82, 170.29, [M + H]⁺ 1H), 7.30 (d, J = 7.7Hz, 162.97, 160.26, calcd for 2H), 6.94 (dd, J = 7.2, 4.7 Hz, 159.68,145.75, C₂₇H₃₅O₈N₂, 4H), 5.75 (s, 2H), 143.98, 142.44, 515.2388;5.21-5.02 (m, 1H), 4.63 (dt, J = 10.8, 7.5 Hz, 129.59, 120.95, found,1H), 4.22 (t, J = 8.8 Hz, 115.41, 109.60, 89.55, 515.2393 1H), 3.91 (s,3H), 2.41 (dt, J = 12.7, 81.44, 74.84, 56.19, 7.1 Hz, 1H), 2.07 (s, 3H),51.91, 45.00, 33.68, 1.95-1.82 (m, 1H), 1.64 (dd, 27.03, 23.53, 20.89, J= 10.5, 3.9 Hz, 4H), 18.85, 18.38, 11.88 1.47-1.34 (m, 1H), 1.30 (d, J =6.5 Hz, 3H), 1.26-1.21 (m, 1H), 1.17 (s, 1H), 0.88 (t, J = 7.3 Hz, 3H)F137 — — ESIMS ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δm/z 627 1H), 8.26 (d, J = 5.4 Hz, 172.70, 170.27, ([M + H]⁺) 1H),7.43-7.27 (m, 5H), 162.98, 7.08 (td, J = 8.7, 6.7 Hz, 1H), 162.96-159.98(m), 6.93 (d, J = 5.4 Hz, 1H), 161.13 (dd, J = 248.8, 13.1 Hz),6.81-6.72 (m, 2H), 5.73 (s, 2H), 160.25, 145.77, 4.98 (dq, J = 9.2, 6.4Hz, 1H), 143.92, 142.40, 4.81 (d, J = 10.8 Hz, 1H), 137.82, 131.60 (dd,J = 9.2, 4.64 (d, J = 10.9 Hz, 1H), 4.60 (dt, 6.7 Hz), 128.53, J = 10.9,7.3 Hz, 1H), 3.89 (s, 127.91, 127.67, 3H), 3.40 (t, J = 9.0 Hz, 1H),123.17 (dd, J = 16.0, 3.8 Hz), 3.12-2.93 (m, 1H), 2.50 (dd, 111.06 (dd,J = 20.7, J = 13.6, 11.5 Hz, 1H), 3.9 Hz), 109.64, 2.39-2.27 (m, 1H),2.06 (s, 3H), 104.33-103.29 (m), 1.94 (ddq, J = 12.2, 8.0, 3.9 Hz,89.49, 83.96, 75.39, 1H), 1.70-1.57 (m, 2H), 74.97, 56.20, 51.79, 1.52(d, J = 6.4 Hz, 3H), 44.52, 33.59, 29.35, 1.49-1.38 (m, 1H), 1.30-1.17(m, 27.15, 20.89, 18.89, 1H), 1.01-0.90 (m, 1H) 18.27 ¹⁹F NMR (CDCl₃) δ−113.32 (d, J = 6.4 Hz), −113.57 (d, J = 6.7 Hz) F138 — — HRMS-ESI ¹HNMR (CDCl₃) δ 8.37 (d, J = 7.9 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.29 (d,J = 5.4 Hz, 172.69, 170.29, [M + H]⁺ 1H), 7.36-7.28 (m, 2H), 163.00,160.27, calcd for 7.05-6.91 (m, 4H), 158.93, 145.77, C₂₇H₃₃O₈N₂F₂,6.03-5.67 (m, 1H), 5.75 (s, 2H), 144.00, 142.31, 551.2199; 5.11 (dq, J =9.1, 6.5 Hz, 1H), 129.84, 121.56, found, 4.72-4.56 (m, 1H), 4.24 (t, J =8.7 Hz, 116.75, 115.26, 551.2202 1H), 3.92 (s, 3H), 109.65, 89.51,80.58, 2.43 (dt, J = 12.9, 6.6 Hz, 1H), 74.49, 56.20, 51.91, 2.09 (s,1H), 2.07 (s, 3H), 37.61, 35.77, 33.36, 2.06-1.95 (m, 1H), 1.94-1.75 (m,29.42, 20.88, 19.32, 3H), 1.73-1.62 (m, 1H), 18.26 1.41 (q, J = 11.3 Hz,1H), 1.31 (d, J = 6.5 Hz, 3H), 1.29-1.24 (m, 1H) F139 — — ESIMS ¹H NMR(CDCl₃) δ 8.28 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ m/z 625 1H), 8.25 (d, J= 5.3 Hz, 172.62, 170.16, ([M + H]⁺) 1H), 7.09 (d, J = 7.8 Hz, 162.87,160.15, 2H), 7.03 (d, J = 8.1 Hz, 2H), 145.66, 143.82, 6.93 (d, J = 5.4Hz, 1H), 142.30, 137.20, 5.72 (s, 2H), 4.89 (dq, J = 9.2, 6.4 Hz,135.37, 128.99, 1H), 4.56 (dt, J = 10.9, 7.4 Hz, 128.55, 127.06 (q, J =276.1 Hz), 1H), 3.88 (s, 3H), 3.79 (dt, 109.53, J = 8.9, 6.1 Hz, 1H),3.59 (dt, J = 8.8, 89.37, 84.16, 74.79, 6.2 Hz, 1H), 3.17 (t, J = 9.0Hz, 71.57, 56.08, 51.68, 1H), 2.96 (dd, J = 13.3, 45.79, 36.39, 33.52,3.4 Hz, 1H), 30.69 (q, J = 29.1 Hz), 2.41-2.12 (m, 7H), 2.05 (s, 3H),26.57, 22.98 (q, J = 2.9 Hz), 1.91-1.76 (m, 3H), 1.68-1.36 (m, 20.90,20.76, 6H), 1.28-1.12 (m, 1H), 18.71, 18.01 0.92-0.79 (m, 1H) ¹⁹F NMR(CDCl₃) δ −66.35 140 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.13 (d, J = 8.0 Hz,¹³C NMR (CDCl₃) δ (m/z) 1H), 8.07 (d, J = 5.4 Hz, 172.75, 170.21, [M +H]⁺ 1H), 6.76 (d, J = 5.4 Hz, 162.92, 160.21, calcd for 1H), 5.53 (s,2H), 4.69 (dt, J = 9.1, 145.73, 143.86, C₂₉H₄₃O₉N₂, 6.4 Hz, 1H), 4.37(dt, J = 10.7, 142.41, 109.60, 89.45, 563.2963; 7.5 Hz, 1H), 3.71 (s,3H), 83.98, 78.32, 75.39, found, 3.26 (dt, J = 13.1, 6.7 Hz, 4H), 75.28,69.04, 56.17, 563.2959 3.05 (dq, J = 6.5, 3.3 Hz, 2H), 51.80, 40.46,33.60, 2.88 (t, J = 8.9 Hz, 1H), 30.63, 28.16, 20.84, 2.15 (dt, J =13.2, 6.5 Hz, 1H), 19.00, 18.06, 11.07, 1.86 (s, 3H), 1.80 (dp, J =13.0, 4.8, 10.63, 3.14, 2.98, 2.92, 4.0 Hz, 1H), 1.59-1.39 (m, 2.86 3H),1.39-1.25 (m, 2H), 1.22 (d, J = 6.4 Hz, 3H), 1.13 (q, J = 11.5 Hz, 1H),0.95-0.77 (m, 3H), 0.43-0.23 (m, 4H), 0.00 (dq, J = 10.1, 5.2, 4.5 Hz,4H) F141 40-45 — ESIMS ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.1 Hz, ¹³C NMR(CDCl₃) δ m/z 655 1H), 8.25 (d, J = 5.3 Hz, 172.62, 170.17, ([M + H]⁺)1H), 7.31-7.23 (m, 2H), 162.88, 161.27 (dd, J = 246.7, 7.23-7.07 (m,4H), 6.93 (d, J = 5.4 Hz, 12.2 Hz), 1H), 6.85-6.72 (m, 161.05 (dd, J =248.0, 2H), 5.73 (s, 2H), 4.91 (dq, J = 9.2, 12.2 Hz), 160.15, 6.4 Hz,1H), 4.57 (dt, J = 10.9, 145.67, 143.83, 7.5 Hz, 1H), 3.89 (s, 3H),142.33, 141.66, 3.78 (dt, J = 8.8, 6.3 Hz, 1H), 131.50 (dd, J = 9.3, 6.6Hz), 3.57 (dt, J = 8.9, 6.5 Hz, 1H), 128.29, 128.24, 3.18 (t, J = 9.0Hz, 1H), 125.79, 123.19 (dd, J = 16.0, 2.98 (d, J = 12.8 Hz, 1H), 2.73(td, 3.8 Hz), J = 7.5, 4.0 Hz, 2H), 2.47 (dd, 110.96 (dd, J = 20.8, 3.7Hz), J = 13.5, 11.5 Hz, 1H), 109.54, 2.31 (ddd, J = 13.2, 6.7, 4.9 Hz,103.97-103.18 (m), 89.40, 1H), 2.06 (s, 3H), 83.99, 74.96, 72.86,2.00-1.80 (m, 3H), 1.68-1.51 (m, 2H), 56.10, 51.68, 44.45, 1.49-1.36 (m,4H), 33.51, 32.33, 31.87, 1.28-1.15 (m, 1H), 0.91 (ddt, J = 14.5, 29.30,27.05, 20.79, 6.4, 3.0 Hz, 1H) 18.76, 18.04 ¹⁹F NMR (CDCl₃) δ −113.37(d, J = 6.6 Hz), −113.58 (d, J = 7.5 Hz) F142 — — HRMS-ESI ¹H NMR(CDCl₃) δ 8.33 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.27 (d, J =5.4 Hz, 172.76, 170.26, [M + H]⁺ 1H), 7.39-7.19 (m, 2H), 162.96, 160.24,calcd for 6.98-6.92 (m, 2H), 158.86, 145.76, C₃₁H₄₁O₉N₂, 6.92-6.86 (m,2H), 5.74 (s, 2H), 143.92, 142.44, 585.2807; 5.07-4.84 (m, 1H), 4.59(dt, J = 10.7, 129.41, 120.59, found, 7.4 Hz, 1H), 114.48, 109.61,89.51, 585.2816 4.16-3.96 (m, 2H), 3.90 (s, 3H), 83.95, 78.24, 75.25,3.49 (dd, J = 9.6, 7.3 Hz, 1H), 66.18, 56.19, 51.83, 3.42 (dd, J = 9.6,6.8 Hz, 1H), 40.33, 33.61, 30.34, 3.14 (t, J = 8.8 Hz, 1H), 28.17,20.88, 19.10, 2.36 (dt, J = 13.2, 6.7 Hz, 1H), 18.10, 11.09, 3.16, 2.19(ddd, J = 15.0, 5.8, 2.3 Hz, 2.94 1H), 2.07 (s, 3H), 1.90-1.75 (m, 2H),1.69 (dq, J = 21.9, 7.6, 7.0 Hz, 2H), 1.62-1.50 (m, 1H), 1.44 (d, J =6.4 Hz, 3H), 1.34 (q, J = 11.5 Hz, 1H), 1.07 (dt, J = 12.1, 5.9 Hz, 2H),0.60-0.49 (m, 2H), 0.21 (q, J = 4.9 Hz, 2H) F143 — — HRMS-ESI ¹H NMR(CDCl₃) δ 8.42 (d, J = 6.9 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.27 (dt, J= 5.0, 173.64, 170.23, [M + H]⁺ 2.6 Hz, 1H), 162.85, 160.26, calcd for7.07-6.83 (m, 1H), 5.82-5.59 (m, 2H), 145.75, 143.93, C₂₁H₂₉O₂N₈,5.10-4.89 (m, 1H), 142.43, 109.60, 89.53, 437.1918; 4.64-4.43 (m, 1H),4.04-3.87 (m, 86.83, 73.26, 67.69, found, 3H), 3.80 (s, 1H), 3.69 (dq, J= 8.7, 56.18, 53.28, 39.69, 437.1929 5.3, 4.7 Hz, 1H), 3.42 (dd, 36.09,35.75, 32.41, J = 8.2, 3.6 Hz, 1H), 2.38 (t, J = 11.9 Hz, 21.78, 20.85,18.37 1H), 2.12-2.04 (m, 3H), 2.05-1.83 (m, 3H), 1.74 (d, J = 14.6 Hz,1H), 1.64 (t, J = 12.7 Hz, 1H), 1.50 (d, J = 9.5 Hz, 2H), 1.46-1.32 (m,4H) F144 76-80 — ESIMS ¹H NMR (CDCl₃) δ 8.28 (d, J = 7.9 Hz, ¹³C NMR(CDCl₃) δ m/z 631 1H), 8.22 (d, J = 5.4 Hz, 172.51, 170.12, ([M + H]⁺)1H), 7.58 (dd, J = 1.9, 0.6 Hz, 162.84, 161.37 (dd, J = 246.6, 1H), 7.15(dd, J = 3.4, 0.6 Hz, 11.6 Hz), 1H), 7.02 (td, J = 8.5, 6.4 Hz, 160.88(dd, J = 247.6, 1H), 6.92 (d, J = 5.4 Hz, 11.5 Hz), 160.13, 1H),6.73-6.62 (m, 2H), 158.06, 146.83, 6.50 (dd, J = 3.5, 1.7 Hz, 1H),145.59, 143.86, 5.70 (s, 2H), 5.18 (t, J = 9.2 Hz, 143.79, 142.14, 1H),5.09 (dq, J = 9.5, 6.3 Hz, 131.49 (dd, J = 9.5, 6.5 Hz), 1H), 4.60 (dt,J = 10.9, 7.4 Hz, 122.36 (dd, J = 15.7, 1H), 3.86 (s, 3H), 2.70 (dd, J =13.9, 3.8 Hz), 118.50, 4.5 Hz, 1H), 2.49 (dd, J = 13.9, 111.88, 110.81(dd, J = 21.0, 10.2 Hz, 1H), 3.7 Hz), 2.34 (ddt, J = 13.2, 7.4, 3.7 Hz,109.55, 103.56 (t, J = 25.7 Hz), 1H), 2.18-2.07 (m, 1H), 89.32, 76.33,2.03 (s, 3H), 1.73-1.51 (m, 3H), 72.97, 56.06, 51.59, 1.29 (d, J = 6.3Hz, 3H), 42.51, 33.26, 29.97, 1.27-1.18 (m, 1H), 1.12-0.98 (m, 27.25,20.72, 18.65, 1H) 17.38 ¹⁹F NMR (CDCl₃) δ −112.99 (d, J = 6.8 Hz),−113.49 (d, J = 6.9 Hz) F145 48-53 — ESIMS ¹H NMR (CDCl₃) δ 8.28 (d, J =8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 593 1H), 8.25 (d, J = 5.4 Hz, 172.33,169.88, ([M + H]⁺) 1H), 7.11 (td, J = 8.5, 6.5 Hz, 162.58, 160.96 (dd, J= 246.6, 1H), 6.92 (d, J = 5.4 Hz, 12.1 Hz), 1H), 6.82-6.71 (m, 2H),160.77 (dd, J = 247.7, 5.72 (s, 2H), 4.89 (dq, J = 9.2, 6.4 Hz, 11.9Hz), 159.86, 1H), 4.57 (ddd, J = 10.9, 145.37, 143.54, 8.1, 7.0 Hz, 1H),3.88 (s, 3H), 142.06, 131.51 3.54 (dd, J = 8.4, 6.2 Hz, 1H), −130.92(m), 3.31 (dd, J = 8.4, 6.5 Hz, 1H), 122.97 (dd, J = 16.0, 3.8 Hz), 3.15(t, J = 9.0 Hz, 1H), 110.65 (dd, J = 20.8, 3.04-2.93 (m, 1H), 2.46 (dd,J = 13.5, 3.9 Hz), 109.22, 11.6 Hz, 1H), 2.30 (dtd, J = 13.1,103.94-102.92 (m), 6.6, 1.9 Hz, 1H), 89.12, 83.23, 80.04, 2.05 (s, 3H),1.94-1.77 (m, 2H), 74.80, 55.80, 51.38, 1.66-1.51 (m, 2H), 44.35, 33.25,28.85, 1.49-1.34 (m, 4H), 1.31-1.14 (m, 28.83, 26.71, 20.49, 2H), 0.95(d, J = 6.7 Hz, 3H), 19.10, 19.07, 18.47, 0.94 (d, J = 6.7 Hz, 3H) 17.76¹⁹F NMR (CDCl₃) δ −113.49 (d, J = 6.7 Hz), −113.61 (d, J = 7.0 Hz) F146— — HRMS-ESI ¹H NMR (CDCl₃) δ 8.35 (d, J = 7.9 Hz, ¹³C NMR (CDCl₃) δ(m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.84, 170.31, [M + H]⁺ 1H), 7.26 (s,2H), 162.97, 159.33, calcd for 6.93 (ddd, J = 7.8, 5.4, 4.2 Hz, 4H),145.75, 138.53, C₂H₃₃N₂O₈, 5.84-5.75 (m, 1H), 5.75 (s, 129.49, 121.09,513.2231; 2H), 5.15 (dq, J = 9.1, 6.4 Hz, 116.19, 115.78, found, 1H),5.04 (dt, J = 17.1, 1.3 Hz, 109.61, 99.97, 89.55, 513.2255 1H), 4.95 (d,J = 10.3 Hz, 1H), 80.48, 74.48, 56.19, 4.64 (ddd, J = 11.0, 7.9, 6.7 Hz,51.95, 47.50, 33.61, 1H), 4.31 (t, J = 8.8 Hz, 31.11, 20.89, 19.77, 1H),3.91 (s, 3H), 18.33 2.59-2.46 (m, 1H), 2.46-2.34 (m, 1H), 2.07 (s, 3H),1.90 (td, J = 14.5, 6.7 Hz, 1H), 1.83-1.68 (m, 2H), 1.47-1.36 (m, 2H),1.34 (d, J = 6.4 Hz, 3H) F147 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.41(d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3383, (m/z) 1H), 8.28 (d, J = 5.4 Hz,176.24, 172.82, 2928, ([M]⁺) 1H), 7.33-7.23 (m, 2H), 162.94, 160.23,1746, calcd for 7.00-6.89 (m, 4H), 159.72, 145.61, 1677, C₃₂H₄₄N₂O₈,5.82-5.72 (m, 2H), 5.14-5.01 (m, 144.17, 142.09, 1493, 584.3098; 1H),4.62 (ddd, J = 10.8, 8.0, 129.57, 120.95, 1207 found, 6.9 Hz, 1H),4.26-4.16 (m, 115.50, 109.56, 89.88, 584.3108 1H), 3.89 (s, 3H), 2.55(hept, J = 7.0 Hz, 81.64, 74.86, 56.14, 1H), 2.47-2.32 (m, 51.91, 43.23,36.41, 1H), 1.94-1.31 (m, 7H), 33.86, 33.65, 28.27, 1.30 (d, J = 6.5 Hz,3H), 27.88, 27.56, 23.04, 1.28-1.04 (m, 4H), 1.14 (d, J = 7.0 Hz, 22.06,18.94, 18.68, 6H), 0.80 (d, J = 6.6 Hz, 18.40 3H), 0.79 (d, J = 6.6 Hz,3H) F148 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.39 (d, J = 8.1 Hz, ¹³C NMR(CDCl₃) δ 3379, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 176.21, 172.86, 2925,([M]⁺) 1H), 6.94 (d, J = 5.3 Hz, 162.90, 160.21, 1743, calcd for 1H),5.82-5.72 (m, 2H), 145.60, 144.11, 1677, C₃₀H₄₈N₂O₈, 4.94-4.81 (m, 1H),4.57 (ddd, J = 10.7, 142.15, 109.51, 89.88, 1504, 564.3411; 8.1, 7.0 Hz,1H), 3.89 (s, 84.32, 80.43, 75.43, 1209 found, 3H), 3.46 (dd, J = 8.3,6.3 Hz, 56.12, 51.86, 43.55, 564.3413 1H), 3.27 (dd, J = 8.4, 6.5 Hz,36.55, 33.84, 33.70, 1H), 3.07-2.94 (m, 1H), 29.18, 28.11, 28.04, 2.55(hept, J = 7.0 Hz, 1H), 27.56, 22.98, 22.28 2.42-2.27 (m, 1H), 1.94-1.43(m, 19.52, 19.46, 18.86, 7H), 1.41 (d, J = 6.4 Hz, 3H), 18.67, 18.171.38-0.95 (m, 5H), 1.14 (d, J = 7.0 Hz, 6H), 0.95-0.81 (m, 12H) F149 —(Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.38 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ3382, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 176.22, 172.83, 2927, ([M]⁺) 1H),6.94 (d, J = 5.4 Hz, 162.91, 160.22, 1745, calcd for 1H), 5.81-5.72 (m,2H), 145.61, 144.12, 1678, C₃₀H₄₆N₂O₈, 4.96-4.82 (m, 1H), 4.57 (ddd, J =10.7, 142.15, 109.51, 89.88, 1505, 562.3254; 8.1, 7.0 Hz, 1H), 3.89 (s,84.36, 78.64, 75.39, 1374, found, 3H), 3.58-3.31 (m, 2H), 56.13, 51.83,43.60, 1210 562.3262 3.09-2.97 (m, 1H), 2.55 (hept, J = 7.0 Hz, 36.44,33.85, 33.72, 1H), 2.40-2.29 (m, 28.08, 27.35, 23.03, 1H), 1.86-1.45 (m,6H), 22.22, 18.75, 18.67, 1.42 (d, J = 6.4 Hz, 3H), 18.11, 11.13, 3.08,1.38-0.93 (m, 6H), 1.14 (d, J = 7.0 Hz, 3.01 6H), 0.90 (d, J = 6.6 Hz,3H), 0.88 (d, J = 6.6 Hz, 3H), 0.62-0.50 (m, 2H), 0.27-0.15 (m, 2H) F150— (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.38 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃)δ 3385, (m/z) 1H), 8.27 (d, J = 5.3 Hz, 176.24, 172.82, 2950, ([M]⁺)1H), 6.94 (d, J = 5.4 Hz, 162.93, 160.24, 1746, calcd for 1H), 5.81-5.72(m, 2H), 145.61, 144.16, 1679, C₃₀H₄₅F₃N₂O₈, 4.93-4.81 (m, 1H), 4.57(ddd, J = 10.7, 142.13, 127.17 (q, J = 276.1 Hz), 1506, 618.3128; 8.1,7.0 Hz, 1H), 3.89 (s, 109.52, 1377, found, 3H), 3.80-3.66 (m, 1H),89.90, 84.85, 75.02, 1253 618.3154 3.64-3.50 (m, 1H), 3.09-2.98 (m,71.55, 56.13, 51.85, 1H), 2.55 (hept, J = 7.0 Hz, 43.48, 36.49, 33.86,1H), 2.40-2.28 (m, 1H), 33.66, 30.82 (q, J = 29.0 Hz), 2.28-2.11 (m,2H), 1.88-1.27 (m, 28.20, 28.09, 9H), 1.40 (d, J = 6.4 Hz, 3H), 27.47,23.06 (dd, J = 6.5, 1.27-0.92 (m, 4H), 1.14 (d, J = 7.0 Hz, 3.4 Hz),22.97, 6H), 0.92-0.83 (m, 22.18, 18.84, 18.67, 6H) 18.14 ¹⁹F NMR (CDCl₃)δ −66.43 F151 122-124 — ESIMS ¹H NMR (CDCl₃) δ 8.36 (d, J = 7.2 Hz, ¹³CNMR (CDCl₃) δ m/z 585.5 1H), 8.31 (d, J = 5.4 Hz, 176.39, 170.64, ([M +H]⁺) 1H), 7.31-7.24 (m, 2H), 162.92, 160.31, 7.21-7.15 (m, 3H), 6.97 (d,J = 5.4 Hz, 145.61, 144.44, 1H), 5.76 (s, 2H), 142.06, 140.87, 5.04-4.92(m, 1H), 4.60 (dd, 128.87, 128.36, J = 7.3, 3.8 Hz, 1H), 3.90 (s,125.91, 109.53, 89.99, 3H), 3.54 (dd, J = 8.3, 6.3 Hz, 84.01, 80.55,75.32, 1H), 3.39-3.30 (m, 1H), 56.17, 52.13, 45.78, 3.20-3.10 (m, 2H),37.01, 33.87, 31.97, 2.62-2.49 (m, 1H), 2.40-2.28 (m, 1H), 29.26, 26.94,19.55, 2.00-1.80 (m, 3H), 19.50, 18.69, 18.16, 1.75-1.62 (m, 1H), 1.56(dd, J = 13.8, 17.44 7.4 Hz, 1H), 1.48-1.41 (m, 4H), 1.26 (dd, J = 8.1,6.2 Hz, 1H), 1.22-1.17 (m, 1H), 1.15 (dd, J = 4.9, 2.1 Hz, 6H),0.99-0.93 (m, 7H), 0.93-0.86 (m, 1H) F152 — — ESIMS ¹H NMR (CDCl₃) δ8.34 (d, J = 8.1 Hz, ¹³C NMR (75 MHz, m/z 583.6 1H), 8.25 (d, J = 5.4Hz, CDCl₃) δ 176.36, ([M + H]⁺) 1H), 7.35-7.24 (m, 2H), 172.91, 163.12,7.22-7.13 (m, 3H), 6.93 (d, J = 5.4 Hz, 160.42, 145.79, 1H), 5.82-5.68(m, 144.30, 142.34, 2H), 4.93 (dq, J = 9.1, 6.4 Hz, 140.94, 129.07, 1H),4.58 (ddd, J = 10.8, 8.1, 128.54, 126.08, 7.0 Hz, 1H), 3.88 (s, 3H),109.74, 90.05, 84.04, 3.59 (dd, J = 9.6, 7.0 Hz, 1H), 78.91, 75.41,56.33, 3.45 (dd, J = 9.7, 6.8 Hz, 1H), 54.04, 51.98, 46.25, 3.26-3.07(m, 2H), 2.54 (p, J = 7.0 Hz, 37.12, 34.06, 33.91, 1H), 2.43-2.23 (m,2H), 29.49, 26.85, 19.02, 1.97-1.79 (m, 1H), 18.87, 18.32, 11.39,1.69-1.51 (m, 2H), 1.49-1.38 (m, 3.35, 3.21 overlapping, 1H), 1.46 (d, J= 6.4 Hz, 3H), 1.22-1.05 (m, 2H), 1.14 (d, overlapping, J = 7.0 Hz, 6H),0.95-0.80 (m, 1H), 0.65-0.53 (m, 2H), 0.33-0.19 (m, 2H) F153 — —HRMS-ESI ¹H NMR (CDCl₃) δ 8.54 (d, J = 8.3 Hz, ¹³C NMR (CDCl₃) δ (m/z)1H), 8.34 (d, J = 5.4 Hz, 172.72, 169.43, [M + H]⁺ 1H), 7.35-7.23 (m,2H), 162.36, 159.77, calcd for 7.00 (d, J = 5.5 Hz, 1H), 159.44, 146.77,C₃₂H₄₃N₂O₈, 6.97-6.89 (m, 3H), 5.07 (dq, J = 9.1, 141.48, 137.34,583.3014; 6.5 Hz, 1H), 4.60 (ddd, J = 10.9, 129.58, 120.93, found, 8.3,6.9 Hz, 1H), 115.56, 109.80, 81.67, 583.3013 4.16 (t, J = 8.7 Hz, 1H),3.90 (s, 74.88, 67.71, 67.59, 3H), 3.81 (t, J = 6.6 Hz, 2H), 58.87,58.79, 56.33, 3.69 (dt, J = 9.2, 5.7 Hz, 1H), 51.66, 42.02, 37.27, 3.41(s, 3H), 2.99 (t, J = 6.6 Hz, 36.85, 34.62, 33.87, 2H), 2.63 (t, J = 6.2Hz, 33.66, 31.77, 27.61, 1H), 2.37 (dt, J = 13.3, 6.6 Hz, 25.05, 19.07,18.38 1H), 1.83 (dh, J = 16.6, 4.8, 4.2 Hz, 3H), 1.77-1.35 (m, 9H), 1.28(d, J = 6.5 Hz, 3H), 1.18-1.07 (m, 1H), 0.98 (ddq, J = 15.6, 12.5, 7.9Hz, 2H) F154 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 8.38 (d, J = 8.2 Hz,Film) (m/z) 1H), 8.27 (d, J = 5.3 Hz, 3381, ([M]⁺) 1H), 6.93 (d, J = 5.4Hz, 2942, calcd for 1H), 5.81-5.61 (m, 2H), 1745, C₃₁H₄₆N₂O₈, 4.89 (dd,J = 9.2, 6.3 Hz, 1H), 1678, 574.3254; 4.57 (dt, J = 11.0, 7.5 Hz, 1H),1506, found, 3.89 (s, 3H), 3.50 (dd, J = 9.6, 7.0 Hz, 974 674.3262 1H),3.36 (dd, J = 9.6, 6.9 Hz, 1H), 3.01 (t, J = 9.0 Hz, 1H), 2.54 (p, J =7.0 Hz, 1H), 2.36 (dd, J = 13.1, 6.8 Hz, 1H), 1.92-1.43 (m, 15H), 1.42(d, J = 6.5 Hz, 2H), 1.35-1.19 (m, 2H), 1.14 (d, J = 7.0 Hz, 3H),1.17-0.92 (m, 5H), 0.62-0.48 (m, 2H), 0.29-0.17 (m, 2H) F155 HRMS-ESI ¹HNMR (CDCl₃) δ 8.42 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d,J = 5.4 Hz, 176.26, 172.85, ([M]⁺) 1H), 7.33-7.23 (m, 2H), 162.94,160.24, calcd for 7.01-6.89 (m, 4H), 159.69, 145.62, C₂₈H₃₆N₂O₈,5.83-5.73 (m, 2H), 5.10 (dq, J = 9.1, 144.19, 142.08, 528.2472; 6.4 Hz,1H), 4.68-4.55 (m, 129.59, 120.99, found, 1H), 4.17 (t, J = 8.8 Hz, 1H),115.49, 109.55, 89.90, 528.2485 3.89 (s, 3H), 2.55 (hept, J = 7.0 Hz,82.30, 74.68, 56.14, 1H), 2.40 (dt, J = 13.0, 51.95, 37.67, 33.86, 6.6Hz, 1H), 2.01-1.85 (m, 33.63, 32.38, 19.27, 1H), 1.70 (dq, J = 16.8,5.4, 18.69, 18.31, 17.77 4.7 Hz, 3H), 1.40 (dt, J = 13.5, 10.6 Hz, 1H),1.31 (d, J = 6.4 Hz, 3H), 1.29-1.22 (m, 1H), 1.15 (d, J = 7.0 Hz, 6H),1.01 (d, J = 6.9 Hz, 3H) F156 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.19 (d, J =8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.06 (d, J = 5.4 Hz, 176.13,172.72, [M + H]⁺ 1H), 6.75 (d, J = 5.4 Hz, 162.87, 160.17, calcd for1H), 5.66-5.50 (m, 2H), 145.59, 144.05, C₃₁H₄₇O₉N₂, 4.70 (dt, J = 9.1,6.4 Hz, 1H), 142.05, 109.54, 89.79, 591.3276; 4.37 (dt, J = 10.7, 7.4Hz, 1H), 83.98, 78.29, 75.36, found, 3.69 (s, 3H), 3.34-3.18 (m, 4H),75.24, 69.01, 56.11, 591.3280 3.15-3.00 (m, 2H), 2.88 (t, J = 8.8 Hz,51.78, 40.43, 33.79, 1H), 2.34 (p, J = 7.0 Hz, 33.59, 30.63, 28.17, 1H),2.15 (dt, J = 13.1, 6.5 Hz, 19.01, 18.62, 18.04, 1H), 1.81 (dp, J =12.9, 11.06, 10.61, 3.12, 4.8, 4.0 Hz, 1H), 1.48 (td, J = 18.9, 2.96,2.90, 2.85 14.6, 5.7 Hz, 3H), 1.40-1.27 (m, 2H), 1.22 (d, J = 6.4 Hz,3H), 1.13 (q, J = 11.3 Hz, 1H), 0.94 (d, J = 7.0 Hz, 6H), 0.91-0.75 (m,3H), 0.44-0.26 (m, 4H), 0.10-−0.06 (m, 4H) F157 68-72 ESIMS ¹H NMR(CDCl₃) δ 8.34 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ m/z 659 1H), 8.22 (d, J= 5.3 Hz, 176.11, 172.53, ([M + H]⁺) 1H), 7.59 (dd, J = 1.7, 0.8 Hz,162.83, 161.40 (dd, J = 246.3, 1H), 7.15 (dd, J = 3.5, 0.8 Hz, 11.4 Hz,)1H), 7.03 (td, J = 8.5, 6.4 Hz, 160.91 (dd, J = 247.6, 1H), 6.91 (d, J =5.4 Hz, 11.4 Hz), 160.13, 1H), 6.74-6.63 (m, 2H), 158.08, 146.84, 6.50(dd, J = 3.5, 1.7 Hz, 1H), 145.47, 144.12, 5.77-5.70 (m, 2H), 5.19 (t, J= 9.2 Hz, 143.82, 141.83, 1H), 4.61 (dt, J = 10.9, 7.5 Hz, 131.51 (dd, J= 9.3, 6.5 Hz), 1H), 3.85 (s, 3H), 122.39 (dd, J = 15.8, 2.71 (dd, J =13.9, 4.5 Hz, 1H), 3.7 Hz), 118.52, 2.57-2.46 (m, 2H), 2.35 (ddt,111.90, 110.83 (dd, J = 21.0, J = 13.2, 7.7, 3.3 Hz, 1H), 3.6 Hz),2.18-2.07 (m, 1H), 1.74-1.52 (m, 109.50, 103.58 (t, J = 25.7 Hz), 3H),1.34-1.18 (m, 5H), 89.72, 76.37, 1.11 (d, J = 7.0 Hz, 6H) 72.98, 56.02,51.61, 42.53, 33.72, 33.31, 30.00, 27.28, 18.68, 18.55, 17.41 ¹⁹F NMR(CDCl₃) δ −113.00 (d, J = 7.1 Hz), −113.49 (d, J = 6.7 Hz) F158 — (Neat)HRMS-ESI ¹H NMR (CDCl₃) δ 8.37 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 2926,(m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.79, 170.04, 1746, ([M]⁺) 1H),7.35-7.23 (m, 2H), 162.91, 160.16, 1678, calcd for 6.99-6.91 (m, 4H),5.82 (s, 159.70, 145.80, 1494, C₃₂H₄₄N₂O₉, 2H), 5.14-5.01 (m, 1H),143.89, 142.25, 1208, 600.3047; 4.67-4.54 (m, 1H), 4.25-4.17 (m, 129.57,120.95, 1098 found, 1H), 4.10 (s, 2H), 3.90 (s, 3H), 115.48, 109.73,89.50, 600.3070 3.59 (q, J = 7.0 Hz, 2H), 81.62, 74.86, 67.78, 2.47-2.31(m, 1H), 1.98-1.31 (m, 67.16, 56.23, 51.90, 7H), 1.30 (d, J = 6.4 Hz,3H), 43.20, 36.39, 33.61, 1.27-1.03 (m, 4H), 1.23 (t, J = 7.0 Hz, 28.26,27.87, 27.58, 3H), 0.80 (d, J = 6.7 Hz, 23.03, 22.05, 18.94, 3H), 0.79(d, J = 6.6 Hz, 18.39, 15.01 3H) F159 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ8.35 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 2954 (m/z) 1H), 8.27 (d, J = 5.4Hz, 172.83, 170.03, 1744, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.86,160.14, 1679, calcd for 1H), 5.82 (s, 2H), 145.78, 143.85, 1506,C₃₀H₄₈N₂O₉, 4.94-4.81 (m, 1H), 4.63-4.49 (m, 1H), 142.34, 109.66, 89.53,1210, 580.3360; 4.10 (s, 2H), 3.90 (s, 3H), 84.31, 80.43, 75.45, 1096found, 3.59 (q, J = 7.0 Hz, 2H), 3.46 (dd, J = 8.4, 67.78, 67.16, 56.20,580.3379 6.3 Hz, 1H), 3.27 (dd, J = 8.4, 51.85, 43.53, 36.55, 6.5 Hz,1H), 33.68, 29.18, 28.11, 3.06-2.96 (m, 1H), 2.41-2.26 (m, 1H), 28.03,27.58, 22.97, 1.92-1.42 (m, 7H), 1.41 (d, J = 6.4 Hz, 22.28, 19.51,19.46, 3H), 1.38-0.95 (m, 18.85, 18.17, 15.00 5H), 1.23 (t, J = 7.0 Hz,3H), 0.95-0.82 (m, 12H) F160 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d,J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3378, (m/z) 1H), 8.27 (d, J = 5.5 Hz,172.81, 170.04, 2948, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.88, 160.15,1741, calcd for 1H), 5.82 (s, 2H), 145.80, 143.85, 1676, C₃₀H₄₆N₂O₉,4.95-4.82 (m, 1H), 4.55 (ddd, J = 10.7, 142.34, 109.68, 89.53, 1504,578.3203; 8.2, 7.0 Hz, 1H), 4.10 (s, 2H), 84.36, 78.63, 75.41, 1374,found, 3.90 (s, 3H), 3.59 (q, J = 7.0 Hz, 67.78, 67.17, 56.21, 1209578.3206 2H), 3.51 (dd J = 9.7, 7.0 Hz, 51.83, 43.58, 36.43, 1H), 3.38(dd J = 9.7, 6.9 Hz, 33.69, 28.07, 27.37, 1H), 3.09-2.97 (m, 1H), 23.03,22.21, 18.75, 2.40-2.27 (m, 1H), 18.11, 15.00, 11.13 1.84-1.45 (m, 6H),1.42 (d, J = 6.4 Hz, 3.08, 3.01 3H), 1.38-0.92 (m, 6H), 1.23 (t, J = 7.0Hz, 3H), 0.90 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H), 0.62-0.50(m, 2H), 0.28-0.16 (m, 2H) F161 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.34(d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3378, (m/z) 1H), 8.27 (d, J = 5.3 Hz,172.84, 170.04, 2933, ([M]⁺) 1H), 6.94 (d, J = 5.4 Hz, 162.88, 160.16,1742, calcd for 1H), 5.82 (s, 2H), 145.78, 143.88, 1677, C₂₉H₄₆N₂O₉,4.93-4.81 (m, 1H), 4.56 (ddd, J = 10.8, 142.36, 109.66, 89.56, 1504,566.3203; 8.1, 7.0 Hz, 1H), 4.10 (s, 2H), 84.58, 75.42, 67.79, 1374,found, 3.90 (s, 3H), 3.69-3.57 (m, 67.17, 56.21, 51.85, 1128 566.32371H), 3.59 (q, J = 7.0 Hz, 2H), 43.52, 36.51, 33.71, 3.51-3.41 (m, 1H),28.10, 27.52, 23.54, 3.07-2.98 (m, 1H), 2.41-2.27 (m, 23.02, 22.22,18.82, 1H), 1.82-1.27 (m, 9H) 18.12, 15.00, 10.70 1.42 (d, J = 6.4 Hz,3H), 1.27-0.95 (m, 4H), 1.23 (t, J = 7.0 Hz, 3H), 0.94 (t, J = 7.4 Hz,3H), 0.89 (d, J = 6.6 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H) F162 — (Neat)HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3377,(m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.80, 170.05, 2950, ([M]⁺) 1H), 6.95(d, J = 5.4 Hz, 162.90, 160.17, 1744, calcd for 1H), 5.82 (s, 2H),145.79, 143.90, 1678, C₃₀H₄₅F₃N₂O₉, 4.93-4.81 (m, 1H), 4.56 (ddd, J =10.7, 142.31, 127.17 (q, J = 275.9 Hz), 1505, 634.3077; 8.0, 6.9 Hz,1H), 4.10 (s, 2H), 109.69, 1314, found, 3.90 (s, 3H), 3.79-3.69 (m,89.55, 84.85, 75.05, 1130 634.3089 1H), 3.63-3.52 (m, 1H), 71.55, 67.79,67.18, 3.59 (q, J = 7.0 Hz, 2H), 56.21, 51.84, 43.46, 3.09-2.98 (m, 1H),2.40-2.28 (m, 36.48, 33.64, 30.82 (q, 1H), 2.28-2.12 (m, 2H), J = 29.1Hz), 28.20, 1.89-1.27 (m, 9H), 1.40 (d, J = 6.4 Hz, 28.09, 27.48, 23.06(q, 3H), 1.27-0.94 (m, 4H), J = 3.0 Hz), 22.96, 1.23 (t, J = 7.0 Hz,3H), 22.17, 18.84, 18.14, 0.93-0.83 (m, 6H) 15.00 ¹⁹F NMR (CDCl₃) δ−66.44 F163 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³CNMR (CDCl₃) δ 3379, (m/z) 1H), 8.27 (d, J = 5.3 Hz, 172.77, 170.03,2941, ([M]⁺) 1H), 6.95 (d, J = 5.4 Hz, 162.87, 160.15, 1743, calcd for1H), 5.82 (s, 2H), 145.78, 143.86, 1678, C₂₇H₄₂N₂O₉, 4.92-4.80 (m, 1H),4.62-4.50 (m, 1H), 142.32, 109.68, 89.51, 1504, 538.2890; 4.10 (s, 2H),3.90 (s, 3H), 86.41, 75.14, 67.77, 1374, found, 3.59 (q, J = 7.0 Hz,2H), 3.50 (s, 67.15, 61.18, 56.21, 1210 538.2903 3H), 2.99-2.89 (m, 1H),51.80, 43.53, 36.47, 2.41-2.26 (m, 1H), 1.83-1.27 (m, 33.67, 28.24,28.14, 7H), 1.43 (d, J = 6.4 Hz, 3H), 27.26, 23.07, 22.16, 1.27-0.92 (m,4H), 1.23 (t, J = 7.0 Hz, 18.75, 18.05, 14.99 3H), 0.90 (d, J = 6.6 Hz,3H), 0.88 (d, J = 6.6 Hz, 3H) F164 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ8.30 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ 3381, (m/z) 1H), 8.26 (d, J = 5.4Hz, 172.66, 170.01, 2938, ([M]⁺) 1H), 7.17-7.09 (m, 2H), 162.89, 161.26(d, J = 243.6 Hz), 1742, calcd for 7.02-6.91 (m, 3H), 5.81 (s, 160.14,1677, C₃₂H₄₁FN₂O₉, 2H), 4.99-4.84 (m, 1H), 145.79, 143.83, 1507,616.2796; 4.56 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.25, 136.32 (d, J = 3.2Hz), 1314, found, 1H), 4.09 (s, 2H), 3.90 (s, 3H), 130.14 (d, J = 7.7Hz), 1218 616.2815 3.64-3.53 (m, 3H), 3.45 (dd, 115.10 (d, J = 21.0 Hz),J = 9.7, 6.8 Hz, 1H), 3.17 (t, J = 9.0 Hz, 109.71, 1H), 3.14-3.05 (m,89.48, 83.72, 78.75, 1H), 2.37-2.23 (m, 2H), 75.18, 67.76, 67.14,1.89-1.77 (m, 1H), 1.63-1.50 (m, 56.21, 51.73, 46.13, 2H), 1.47-1.34 (m,1H), 36.04, 33.60, 26.62, 1.46 (d, J = 6.5 Hz, 3H), 18.77, 18.08, 14.99,1.32-1.05 (m, 2H), 1.22 (t, J = 7.0 Hz, 11.16, 3.13, 2.99 3H), 0.95-0.80(m, 1H), ¹⁹F NMR (CDCl₃) δ −117.49 0.65-0.52 (m, 2H), 0.31-0.19 (m, 2H)F165 68-70 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.0 Hz, ¹³C NMR(CDCl₃) δ 3379, (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.67, 170.04, 2938,([M]⁺) 1H), 7.35-7.25 (m, 2H), 162.92, 161.30 (d, J = 243.7 Hz), 1744,calcd for 7.13-6.87 (m, 8H), 5.82 (s, 160.17, 1676, C₃₄H₃₉FN₂O₉, 2H),5.18-5.05 (m, 1H), 159.55, 145.80, 1507, 638.2640; 4.62 (ddd, J = 11.0,8.1, 6.9 Hz, 143.91, 142.21, 1206 found, 1H), 4.38-4.29 (m, 1H), 135.84(d, J = 3.1 Hz), 638.2663 4.10 (s, 2H), 3.90 (s, 3H), 3.59 (q, J = 7.0Hz, 130.10 (d, J = 7.7 Hz), 2H), 3.03-2.91 (m, 129.72, 121.25, 1H),2.42-2.28 (m, 2H), 115.46, 115.11 (d, J = 21.1 Hz), 2.12-1.99 (m, 1H),1.73-1.61 (m, 109.74, 2H), 1.61-1.46 (m, 1H), 89.50, 80.99, 74.62, 1.35(d, J = 6.5 Hz, 3H), 67.79, 67.16, 56.22, 1.30-1.23 (m, 1H), 1.22 (t, J= 7.0 Hz, 51.82, 45.71, 36.11, 3H), 1.11-0.97 (m, 1H) 33.55, 26.81,18.95, 18.35, 15.00 ¹⁹F NMR (CDCl₃) δ −117.34 F166 — (Neat) HRMS-ESI ¹HNMR (CDCl₃) δ 8.30 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3377, (m/z) 1H),8.26 (d, J = 5.3 Hz, 172.69, 170.04, 2939, ([M]⁺) 1H), 7.18-7.06 (m,2H), 162.91, 161.30 (d, J = 243.6 Hz), 1743, calcd for 7.03-6.90 (m,3H), 160.17, 1676, C₃₁H₃₉FN₂O₉, 6.06-5.84 (m, 1H), 5.82 (s, 2H), 145.80,143.89, 1507, 602.2640; 5.33 (dq, J = 17.2, 1.6 Hz, 142.27, 136.26 (d, J= 3.3 Hz), 1220 found, 1H), 5.21 (dq, J = 10.4, 1.3 Hz, 134.30, 602.26481H), 4.98-4.87 (m, 1H), 130.14 (d, J = 7.7 Hz), 4.57 (ddd, J = 10.9,8.1, 7.0 Hz, 117.15, 115.12 (d, J = 21.1 Hz), 1H), 4.29 (ddt, J = 12.3,109.70, 5.5, 1.4 Hz, 1H), 89.53, 84.16, 75.05, 4.16-4.08 (m, 1H), 4.09(s, 2H), 3.90 (s, 74.70, 67.80, 67.18, 3H), 3.59 (q, J = 7.0 Hz, 2H),56.22, 51.76, 45.97, 3.30-3.18 (m, 1H), 36.11, 33.63, 26.63, 3.12-3.01(m, 1H), 2.41-2.24 (m, 18.82, 18.16, 15.01 2H), 1.89-1.75 (m, 1H), ¹⁹FNMR (CDCl₃) δ −117.46 1.63-1.51 (m, 2H), 1.47 (d, J = 6.4 Hz, 3H),1.46-1.36 (m, 1H), 1.28-1.14 (m, 1H), 1.23 (t, J = 7.0 Hz, 3H),0.97-0.81 (m, 1H) F167 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.31 (d, J = 8.1Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.26 (d, J = 5.4 Hz, 172.69, 170.03,([M]⁺) 1H), 7.17-7.07 (m, 2H), 162.89, 161.27 (d, J = 243.6 Hz), calcdfor 7.02-6.90 (m, 3H), 5.81 (s, 160.15, C₃₁H₄₁FN₂O₉, 2H), 4.98-4.83 (m,1H), 145.80, 143.86, 604.2796; 4.57 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.27,136.39 (d, J = 3.2 Hz), found, 1H), 4.09 (s, 2H), 3.90 (s, 3H), 130.13(d, J = 7.7 Hz), 604.2800 3.73 (dt, J = 8.6, 6.5 Hz, 1H), 115.09 (d, J =21.0 Hz), 3.59 (q, J = 7.0 Hz, 2H), 109.70, 3.52 (dt, J = 8.7, 6.7 Hz,1H), 89.51, 83.92, 75.62, 3.20-3.11 (m, 1H), 3.11-3.01 (m, 75.21, 67.78,67.16, 1H), 2.41-2.23 (m, 2H), 56.21, 51.75, 46.15, 1.87-1.72 (m, 1H),1.71-1.51 (m, 36.00, 33.63, 26.63, 4H), 1.46 (d, J = 6.5 Hz, 3H), 23.58,18.81, 18.09, 1.46-1.35 (m, 1H), 15.00, 10.72 1.30-1.14 (m, 1H), 1.23(t, J = 7.0 Hz, ¹⁹F NMR (CDCl₃) δ −117.52 3H), 0.98 (t, J = 7.4 Hz, 3H),0.94-0.79 (m, 1H) F168 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.31 (d, J =8.1 Hz, ¹³C NMR (CDCl₃) δ 3380, (m/z) 1H), 8.26 (d, J = 5.3 Hz, 172.70,170.05, 2956, ([M]⁺) 1H), 7.17-7.06 (m, 2H), 162.90, 161.28 (d, J =243.6 Hz), 1742, calcd for 7.03-6.89 (m, 3H), 5.82 (s, 160.16, 1677,C₃₂H₄₃FN₂O₉, 2H), 4.98-4.83 (m, 1H), 145.80, 143.89, 1507, 618.2953;4.57 (ddd, J = 10.9, 8.1, 7.0 Hz, 142.29, 136.43 (d, J = 3.2 Hz), 1375,found, 1H), 4.09 (s, 2H), 3.90 (s, 3H), 130.13 (d, J = 7.7 Hz), 1220618.2960 3.59 (q, J = 7.0 Hz, 2H), 115.11 (d, J = 21.1 Hz), 3.56 (dd, J= 8.4, 6.3 Hz, 1H), 109.69, 3.33 (dd, J = 8.4, 6.5 Hz, 1H), 89.54,83.66, 80.69, 3.18-3.10 (m, 1H), 3.10-3.00 (m, 75.25, 67.79, 67.18, 1H),2.39-2.23 (m, 2H), 56.22, 51.76, 46.29, 1.97-1.73 (m, 2H), 1.63-1.51 (m,35.91, 33.65, 29.27, 2H), 1.45 (d, J = 6.4 Hz, 3H), 26.59, 19.53, 19.49,1.45-1.33 (m, 1H), 18.85, 18.17, 15.01 1.29-1.14 (m, 1H), 1.23 (t, J =7.0 Hz, ¹⁹F NMR (CDCl₃) δ −117.52 3H), 0.97 (d, J = 6.7 Hz, 3H), 0.96(d, J = 6.7 Hz, 3H), 0.93-0.80 (m, 1H) F169 — (Neat) HRMS-ESI ¹H NMR(CDCl₃) δ 8.30 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.26(d, J = 5.4 Hz, 172.56, 170.04, 2940, ([M]⁺) 1H), 7.18-7.05 (m, 2H),162.92, 161.35 (d, J = 243.8 Hz), 1745, calcd for 7.03-6.90 (m, 3H),5.87 (tt, J = 55.1, 160.17, 1678, C₃₀H₃₇F₃N₂O_(9,) 4.0 Hz, 1H), 5.81 (s,145.81, 143.89, 1508, 626.2451; 2H), 5.00-4.87 (m, 1H), 142.19, 135.85(d, J = 3.2 Hz), 1220 found, 4.56 (ddd, J = 10.9, 8.1, 7.0 Hz, 130.14(d, J = 7.8 Hz), 626.2455 1H), 4.09 (s, 2H), 115.19 (d, J = 21.1 Hz),4.06-3.91 (m, 1H), 3.90 (s, 3H), 113.88 (t, J = 241.2 Hz), 3.87-3.71 (m,1H), 3.59 (q, J = 7.0 Hz, 109.75, 2H), 3.31-3.22 (m, 1H), 89.49, 85.53,74.42, 3.10-2.99 (m, 1H), 72.59 (t, J = 27.6 Hz), 2.44-2.23 (m, 2H),1.92-1.76 (m, 67.78, 67.16, 56.22, 1H), 1.68-1.36 (m, 3H), 51.72, 45.79,35.92, 1.47 (d, J = 6.5 Hz, 3H), 33.50, 26.59, 18.86, 1.30-1.15 (m, 1H),1.23 (t, J = 7.0 Hz, 18.14, 15.00 3H), 0.96-0.81 (m, 1H) ¹⁹F NMR (CDCl₃)δ −117.21, −125.47 (d, J = 9.4 Hz, 2F) F170 — (Neat) HRMS-ESI ¹H NMR(CDCl₃) δ 8.30 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.26(d, J = 5.4 Hz, 176.11, 172.70, 2943, ([M]⁺) 1H), 7.12-7.02 (m, 2H),170.06, 162.89, 1733, calcd for 7.01-6.91 (m, 3H), 5.81 (s, 161.36 (d, J= 244.0 Hz), 1678, C₃₄H₄₃FN₂O₁₀, 2H), 5.10-4.97 (m, 2H), 160.17, 145.75,1508, 658.2902; 4.60 (ddd, J = 10.9, 8.0, 7.0 Hz, 143.96, 142.18, 1156found, 1H), 4.10 (s, 2H), 3.90 (s, 3H), 135.58 (d, J = 3.2 Hz), 658.29053.59 (q, J = 7.0 Hz, 2H), 130.06 (d, J = 7.7 Hz), 2.81-2.69 (m, 1H),2.66 (dd, J = 13.8, 115.22 (d, J = 21.2 Hz), 3.8 Hz, 1H), 109.72, 89.51,75.54, 2.43-2.28 (m, 2H), 2.01-1.45 (m, 11H), 73.17, 67.78, 67.17,1.34-1.17 (m, 2H), 1.29 (d, J = 5.7 Hz, 56.22, 51.73, 44.14, 3H), 1.23(t, J = 7.0 Hz, 44.01, 35.93, 33.43, 3H), 1.05-0.92 (m, 1H) 30.06,30.04, 26.83, 25.72, 25.69, 18.72, 17.55, 15.00 ¹⁹F NMR (CDCl₃) δ−117.11 F171 118-120 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.30 (d, J = 7.9Hz, ¹³C NMR (CDCl₃) δ 3379, (m/z) 1H), 8.26 (d, J = 5.3 Hz, 176.44,172.68, 2976, ([M]⁺) 1H), 7.13-7.02 (m, 2H), 170.05, 162.90, 2939, calcdfor 7.02-6.90 (m, 3H), 5.81 (s, 161.35 (d, J = 244.0 Hz), 1734,C₃₂H₄₁FN₂O₁₀, 2H), 5.12-4.96 (m, 2H), 160.17, 145.75, 1677, 632.2745;4.68-4.54 (m, 1H), 4.10 (s, 2H), 143.94, 142.17, 1507, found, 3.90 (s,3H), 3.59 (q, J = 7.0 Hz, 135.53 (d, J = 3.2 Hz), 1153 632.2746 2H),2.65 (dd, J = 14.0, 130.05 (d, J = 7.8 Hz), 3.6 Hz, 1H), 2.58 (hept, J =7.0 Hz, 115.22 (d, J = 21.1 Hz), 1H), 2.45-2.26 (m, 2H), 109.74, 89.48,75.48, 2.00-1.85 (m, 1H), 73.10, 67.77, 67.16, 1.77-1.43 (m, 3H), 1.29(d, J = 5.6 Hz, 56.22, 51.73, 44.11, 3H), 1.29-1.15 (m, 10H), 35.85,34.21, 33.41, 1.05-0.91 (m, 1H) 26.76, 19.07, 18.98, 18.72, 17.49, 15.00¹⁹F NMR (CDCl₃) δ −117.07 F172 — — ESIMS ¹H NMR (CDCl₃) δ 8.30 (d, J =8.2 Hz, ¹³C NMR (CDCl₃) δ m/z 601.7 1H), 8.26 (d, J = 5.3 Hz, 172.72,170.04, ([M + H]⁺) 1H), 7.33-7.23 (m, 3H), 162.89, 160.15, 7.23-7.13 (m,3H), 6.93 (d, J = 5.4 Hz, 145.78, 143.87, 1H), 5.81 (s, 2H), 142.31,140.85, 4.91 (dq, J = 9.1, 6.4 Hz, 1H), 128.86, 128.34, 4.57 (dt, J =10.9, 7.5 Hz, 1H), 125.87, 109.67, 89.55, 4.09 (s, 2H), 3.90 (s, 3H),83.71, 80.65, 75.30, 3.65-3.51 (m, 3H), 3.34 (dd, J = 8.4, 67.79, 67.18,56.21, 6.5 Hz, 1H), 51.77, 46.19, 36.73, 3.20-3.03 (m, 2H), 2.42-2.21(m, 2H), 33.70, 29.70, 29.28, 1.98-1.76 (m, 2H), 26.56, 19.55, 19.50,1.63-1.53 (m, 2H), 1.50-1.40 (m, 18.84, 18.18, 15.01 overlapping, 1H),1.46 (d, J = 6.4 Hz, 3H), 1.31-1.15 (m, 7H), 0.97 (dd, J = 6.7, 5.2 Hz,6H), 0.92-0.80 (m, 2H) F173 — — ESIMS ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.1Hz, ¹³C NMR (CDCl₃) δ m/z 599.6 1H), 8.26 (d, J = 5.4 Hz, 172.70,170.04, ([M + H]⁺) 1H), 7.38-7.23 (m, 2H), 162.89, 160.15, 7.23-7.15 (m,3H), 6.93 (d, J = 5.4 Hz, 145.79, 143.86, 1H), 5.81 (s, 2H), 142.30,140.72, 4.93 (dq, J = 9.0, 6.4 Hz, 1H), 128.88, 128.35, 4.57 (dt, J =10.9, 7.5 Hz, 1H), 125.90, 109.67, 89.53, 4.09 (s, 2H), 3.90 (s, 3H),83.81, 78.75, 75.25, 3.61-3.52 (m, 3H), 3.45 (dd, J = 9.7, 67.79, 67.18,56.21, 6.8 Hz, 1H), 51.75, 46.05, 36.89, 3.26-3.09 (m, 2H), 2.44-2.22(m, 2H), 33.69, 29.70, 26.60, 1.89 (ddq, J = 12.0, 7.4, 3.7 Hz, 18.77,18.11, 15.01, 1H), 1.57 (ddd, J = 12.3, 11.17, 3.16, 3.01 6.4, 2.5 Hz,2H), 1.51-1.40 (m, overlapping, 1H), 1.46 (d, J = 6.4 Hz, 3H), 1.32-1.18(m, 3H), 1.17-1.10 (m, 1H), 0.96-0.78 (m, 2H), 0.64-0.51 (m, 2H), 0.26(dd, J = 5.8, 3.7 Hz, 2H) F174 — — ESIMS ¹H NMR (CDCl₃) δ 8.30 (d, J =8.1 Hz, ¹³C NMR (CDCl₃) δ m/z 587.5 1H), 8.26 (d, J = 5.3 Hz, 172.72,170.04, ([M + H]⁺) 1H), 7.35-7.23 (m, 2H), 162.89, 160.15, 7.23-7.13 (m,3H), 6.93 (d, J = 5.4 Hz, 145.79, 143.87, 1H), 5.81 (s, 2H), 142.31,140.80, 4.91 (dq, J = 9.2, 6.4 Hz, 1H), 128.87, 128.34, 4.57 (ddd, J =10.9, 8.2, 7.0 Hz, 125.88, 109.68, 89.54, 1H), 4.09 (s, 2H), 3.89 (s,84.00, 75.60, 75.26, 3H), 3.74 (dt, J = 8.7, 6.6 Hz, 67.79, 67.18,56.21, 1H), 3.66-3.47 (m, 3H), 51.76, 46.06, 36.83, 3.18 (t, J = 9.1 Hz,1H), 3.11 (dd, J = 13.3, 33.70, 26.60, 23.59, 3.4 Hz, 1H), 18.81, 18.11,15.01, 2.42-2.23 (m, 2H), 1.85 (ddt, J = 12.1, 10.74 8.2, 3.7 Hz, 1H),1.70-1.53 (m, 4H), 1.51-1.40 (m, overlapping, 1H), 1.46 (d, J = 6.4 Hz,3H), 1.36-1.11 (m, 4H), 0.98 (t, J = 7.4 Hz, 3H), 0.91-0.81 (m, 1H) F175— — ESIMS ¹H NMR (CDCl₃) δ 8.34 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ m/z607.6 1H), 8.27 (d, J = 5.3 Hz, 172.83, 170.05, ([M + H]⁺) 1H), 6.95 (d,J = 5.4 Hz, 162.88, 160.15, 1H), 5.82 (s, 2H), 4.87 (dq, J = 9.2,145.79, 143.87, 6.3 Hz, 1H), 142.35, 109.67, 89.54, 4.61-4.48 (m, 1H),4.10 (s, 2H), 3.90 (s, 84.31, 80.37, 75.49, 3H), 3.59 (q, J = 7.0 Hz,2H), 67.78, 67.17, 56.21, 3.46 (dd, J = 8.4, 6.1 Hz, 1H), 51.85, 40.03,38.13, 3.24 (dd, J = 8.4, 6.7 Hz, 1H), 35.08, 34.58, 33.73, 2.98 (t, J =8.8 Hz, 1H), 32.26, 29.20, 27.45, 2.34 (dt, J = 13.2, 6.7 Hz, 1H),26.69, 26.51, 26.20, 1.83 (dp, J = 13.2, 6.6 Hz, 2H), 19.58, 19.46,18.85, 1.77-1.50 (m, 9H), 1.41 (d, J = 6.4 Hz, 18.16, 15.00 3H),1.39-1.11 (m, 10H), 1.02-0.92 (m, 8H), 0.76 (tt, J = 11.6, 6.3 Hz, 1H)F176 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.37 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃)δ (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.80, 170.06, ([M]⁺) 1H), 7.35-7.23(m, 2H), 162.92, 160.18, calcd for 7.02-6.88 (m, 4H), 5.82 (s, 159.77,145.80, C₃₃H₄₄N₂O₉, 2H), 5.07 (dq, J = 9.2, 6.4 Hz, 143.93, 142.30,612.3047; 1H), 4.61 (ddd, J = 10.8, 8.1, 129.58, 120.94, found, 7.0 Hz,1H), 4.18 (t, J = 8.7 Hz, 115.56, 109.71, 89.55, 612.3053 1H), 4.10 (s,2H), 3.90 (s, 81.66, 74.90, 67.80, 3H), 3.59 (q, J = 7.0 Hz, 2H), 67.19,56.23, 51.93, 2.48-2.34 (m, 1H), 42.03, 37.27, 36.85, 1.93-1.33 (m,14H), 1.30 (d, J = 6.5 Hz, 33.70, 33.66, 31.77, 3H), 1.27-1.19 (m, 3H),27.62, 25.05, 19.11, 1.20-1.06 (m, 1H), 18.40, 15.02 1.07-0.90 (m, 2H)F177 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃)δ (m/z) 1H), 8.26 (d, J = 5.4 Hz, 172.71, 170.04, ([M]⁺) 1H), 7.09 (d, J= 8.6 Hz, 162.89, 160.16, calcd for 2H), 6.93 (d, J = 5.4 Hz, 1H),157.83, 145.79, C₃₃H₄₄N₂O₁₀, 6.83 (d, J = 8.6 Hz, 2H), 143.88, 142.32,628.2996; 5.81 (s, 2H), 4.92 (dq, J = 9.2, 6.4 Hz, 132.68, 129.74,found, 1H), 4.56 (ddd, J = 10.9, 113.78, 109.67, 89.55, 628.3010 8.2,7.0 Hz, 1H), 4.09 (s, 2H), 83.82, 78.76, 75.27, 3.90 (s, 3H), 3.79 (s,3H), 67.80, 67.18, 56.21, 3.59 (q, J = 7.0 Hz, 3H), 3.45 (dd, J = 9.7,55.24, 51.76, 46.18, 6.8 Hz, 1H), 3.16 (t, J = 9.1 Hz, 35.93, 33.72,26.56, 1H), 3.08 (dd, J = 13.2, 18.77, 18.11, 15.02, 3.3 Hz, 1H), 11.18,3.16, 3.01 2.37-2.22 (m, 2H), 1.83 (ddt, J = 12.1, 8.4, 3.8 Hz, 1H),1.67-1.51 (m, 3H), 1.46 (d, J = 6.4 Hz, 3H), 1.26-1.18 (m, 1H), 1.23 (t,J = 7.0 Hz, 3H), 1.17-1.05 (m, 1H), 0.87 (d, J = 15.1 Hz, 1H), 0.62-0.54(m, 2H), 0.31-0.19 (m, 2H) F178 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.34 (d, J= 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.27 (d, J = 5.4 Hz, 172.82,170.05, ([M]⁺) 1H), 6.94 (d, J = 5.4 Hz, 162.89, 160.16, calcd for 1H),5.82 (d, J = 0.8 Hz, 2H), 145.80, 143.89, C₃₁H₄₆N₂O₉, 4.89 (dq, J = 9.3,6.4 Hz, 1H), 142.36, 109.66, 89.58, 590.3203; 4.64-4.43 (m, 1H), 4.10(s, 84.35, 78.54, 75.39, found, 3H), 3.90 (s, 3H), 3.59 (q, J = 7.0 Hz,67.80, 67.19, 56.21, 590.3225 2H), 3.50 (dd, J = 9.6, 51.86, 42.33,37.26, 7.0 Hz, 1H), 3.36 (dd, J = 9.6, 36.90, 33.96, 33.76, 6.8 Hz, 1H),3.00 (t, J = 8.9 Hz, 31.84, 27.54, 25.10, 1H), 2.34 (dt, J = 13.3, 6.8Hz, 25.07, 18.97, 18.10, 1H), 1.93-1.45 (m, 12H), 15.01, 11.14, 3.14,1.42 (d, J = 6.5 Hz, 3H), 2.94 1.37-1.27 (m, 1H), 1.23 (t, J = 7.0 Hz,3H), 1.15-0.90 (m, 4H), 0.62-0.50 (m, 2H), 0.21 (dt, J = 5.9, 4.5 Hz,2H) F179 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.30 (d, J = 8.1 Hz, ¹³C NMR(CDCl₃) δ (m/z) 1H), 8.26 (d, J = 5.3 Hz, 172.73, 170.04, ([M]⁺) 1H),7.08 (d, J = 8.6 Hz, 162.88, 160.15, calcd for 2H), 6.94 (d, J = 5.4 Hz,1H), 157.80, 145.79, C₃₃H₄₆N₂O₁₀, 6.83 (d, J = 8.6 Hz, 2H), 143.87,142.31, 630.3152; 5.81 (s, 2H), 4.91 (dq, J = 9.2, 6.4 Hz, 132.81,129.71, found, 1H), 4.56 (ddd, J = 10.9, 113.76, 109.68, 89.54, 630.31648.1, 7.0 Hz, 1H), 4.09 (s, 2H), 83.71, 80.63, 75.31, 3.89 (s, 3H), 3.78(s, 3H), 67.79, 67.18, 56.22, 3.66-3.50 (m, 3H), 3.34 (dd, J = 8.4,55.23, 51.77, 46.32, 6.5 Hz, 1H), 3.14 (t, J = 9.0 Hz, 35.78, 33.71,29.27, 1H), 3.04 (dd, J = 13.4, 26.53, 19.55, 19.50, 3.2 Hz, 1H), 18.84,18.18, 15.02 2.35-2.23 (m, 2H), 1.97-1.73 (m, 2H), 1.64-1.51 (m, 2H),1.45 (d, J = 6.4 Hz, 3H), 1.30-1.13 (m, 5H), 0.97 (dd, J = 6.7, 5.2 Hz,6H), 0.94-0.79 (m, 1H) F180 50-55 — ESIMS ¹H NMR (CDCl₃) δ 8.28 (d, J =8.1 Hz, m/z 613 1H), 8.25 (s, 1H), ([M + H]⁺) 7.12-7.03 (m, 4H), 6.93(d, J = 5.4 Hz, ¹³C NMR (CDCl₃) δ 1H), 5.80 (s, 2H), 172.65, 169.98,4.91 (dq, J = 9.2, 6.4 Hz, 1H), 162.83, 160.09, 4.55 (ddd, J = 10.9,8.2, 7.0 Hz, 145.74, 143.80, 1H), 4.08 (s, 2H), 3.88 (s, 142.23, 137.49,3H), 3.58 (q, J = 7.0 Hz, 2H), 135.29, 128.98, 3.58 (dd, J = 9.7, 7.0Hz, 1H), 128.68, 109.63, 89.47, 3.44 (dd, J = 9.7, 6.9 Hz, 1H), 83.74,78.69, 75.20, 3.16 (t, J = 9.1 Hz, 1H), 67.73, 67.11, 56.16, 3.09 (dd, J= 13.2, 3.3 Hz, 1H), 51.69, 46.01, 36.33, 2.39-2.21 (m, 5H), 33.64,26.49, 20.96, 1.93-1.80 (m, 1H), 1.63-1.51 (m, 18.69, 18.05, 14.96, 2H),1.51-1.40 (m, 4H), 11.12, 3.10, 2.95 1.30-1.07 (m, 5H), 0.90-0.80 (m,1H), 0.61-0.54 (m, 2H), 0.28-0.20 (m, 2H) F181 — — HRMS-ESI ¹H NMR(CDCl₃) δ 8.35 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.27 (d, J =5.4 Hz, 172.76, 170.06, ([M + Na]⁺) 1H), 6.94 (d, J = 5.5 Hz, 162.90,160.18, calcd for 1H), 5.82 (s, 2H), 4.90 (dq, J = 9.1, 145.80, 143.91,C₂₇H₄₁FN₂O₉Na, 6.4 Hz, 1H), 142.30, 109.69, 89.57, 579.2688; 4.64-4.51(m, 2H), 4.51-4.39 (m, 1H), 83.86, 83.81, 82.17, found 4.10 (s, 2H),3.90 (s, 3H), 80.23, 75.26, 67.80, 579.2694 3.59 (q, J = 7.0 Hz, 2H),3.45 (dd, J = 8.4, 67.19, 56.22, 51.86, 6.6 Hz, 1H), 3.26 (dd, J = 8.4,39.77, 39.73, 33.56, 6.4 Hz, 1H), 31.62, 31.42, 29.17, 3.14-3.02 (m,1H), 2.35 (dt, J = 12.9, 6.7 Hz, 28.72, 19.46, 19.42, 1H), 2.15-1.96 (m,1H), 19.19, 18.14, 15.02 1.83 (dq, J = 13.3, 6.7 Hz, 1H), 1.78-1.60 (m,4H), 1.56 (s, 1H), 1.42 (d, J = 6.4 Hz, 3H), 1.39-1.29 (m, 1H), 1.23 (t,J = 7.0 Hz, 3H), 1.10 (dd, J = 14.0, 6.8 Hz, 1H), 0.96-0.89 (m, 6H) F182— — HRMS-ESI ¹H NMR (CDCl₃) δ 8.37 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ(m/z) 1H), 8.28 (d, J = 5.4 Hz, 172.74, 170.07, ([M + H]⁺) 1H),7.33-7.27 (m, 2H), 162.93, 160.18, calcd for 7.26-7.21 (m, 2H), 159.35,158.78, C₃₅H₄₃N₂O₁₀, 7.02-6.88 (m, 5H), 6.88-6.78 (m, 145.80, 143.96,651.2912; 2H), 5.82 (s, 2H), 142.24, 129.69, found, 5.18-5.06 (m, 1H),4.62 (dt, J = 10.9, 7.0 Hz, 129.39, 121.18, 651.2930 1H), 4.29 (t, J =8.7 Hz, 120.61, 115.42, 1H), 4.10 (s, 2H), 3.96 (t, J = 6.1 Hz, 114.46,109.72, 89.56, 2H), 3.91 (s, 3H), 81.16, 74.79, 67.81, 3.59 (q, J = 7.0Hz, 2H), 2.40 (dt, J = 12.7, 67.19, 66.05, 56.23, 6.7 Hz, 1H), 51.90,40.21, 33.58, 2.15-2.02 (m, 2H), 1.99-1.83 (m, 30.54, 28.47, 19.32, 1H),1.83-1.62 (m, 3H), 18.34, 15.02 1.40 (q, J = 12.3, 11.7 Hz, 1H), 1.32(d, J = 6.5 Hz, 3H), 1.23 (m, 4H) F183 — — HRMS-ESI ¹H NMR (CDCl₃) δ8.37 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.4 Hz,172.74, 170.07, ([M + H]⁺) 1H), 7.32-7.27 (m, 2H), 162.92, 160.18, calcdfor 6.99-6.90 (m, 4H), 5.82 (s, 159.46, 145.80, C₃₀H₄₁N₂O₁₀, 2H), 5.08(dq, J = 9.1, 6.5 Hz, 143.95, 142.27, 589.2756; 1H), 4.61 (dt, J = 10.8,7.0 Hz, 129.62, 121.06, found, 1H), 4.24 (t, J = 8.8 Hz, 1H), 115.38,109.71, 89.56, 589.2763 4.10 (s, 2H), 3.91 (s, 3H), 81.12, 74.84, 70.80,3.59 (q, J = 7.0 Hz, 2H), 3.38 (t, J = 6.8 Hz, 67.80, 67.19, 58.44, 2H),3.26 (s, 3H), 56.23, 51.89, 40.13, 2.40 (dt, J = 12.3, 6.7 Hz, 1H),33.63, 30.56, 28.15, 1.99-1.78 (m, 3H), 1.78-1.61 (m, 19.18, 18.35,15.02 2H), 1.48 (ddd, J = 13.6, 9.9, 6.7 Hz, 1H), 1.39 (q, J = 11.0 Hz,1H), 1.30 (d, J = 6.5 Hz, 3H), 1.23 (t, J = 7.0 Hz, 3H), 1.17 (d, J =7.5 Hz, 1H) F184 — — ESIMS ¹H NMR (CDCl₃) δ 8.52 (d, J = 8.2 Hz, ¹³C NMR(CDCl₃) δ m/z 527.3 1H), 8.34 (d, J = 5.4 Hz, 172.65, 168.71, ([M + H]⁺)1H), 7.00 (d, J = 5.5 Hz, 162.20, 159.41, 1H), 4.89 (dq, J = 9.0, 6.4Hz, 146.89, 141.38, 1H), 4.55 (tt, J = 10.9, 4.4 Hz, 137.00, 109.84,83.85, 2H), 4.48 (s, 2H), 4.44 (ddd, J = 7.7, 83.79, 82.15, 80.20, 5.9,2.6 Hz, 1H), 75.24, 67.86, 67.36, 3.90 (d, J = 1.8 Hz, 3H), 3.73 (q, J =7.0 Hz, 56.30, 51.57, 39.75, 2H), 3.44 (dd, J = 8.4, 33.73, 31.61,31.42, 6.6 Hz, 1H), 3.26 (dd, J = 8.4, 29.17, 28.70, 19.45, 6.4 Hz, 1H),19.41, 19.14, 18.11, 3.10-3.02 (m, 1H), 2.32 (dt, J = 12.9, 6.7 Hz,15.08 1H), 2.13-1.97 (m, 1H), 1.84 (dp, J = 13.2, 6.6 Hz, 1H), 1.78-1.64(m, 3H), 1.60-1.45 (m, 2H), 1.41 (d, J = 6.4 Hz, 3H), 1.37-1.31 (m, 1H),1.29 (t, J = 7.0 Hz, 3H), 1.08 (dd, J = 12.1, 5.0 Hz, 1H), 0.92 (d, J =6.6 Hz, 6H) F185 — — ESIMS ¹H NMR (CDCl₃) δ 8.54 (d, J = 8.2 Hz, ¹³C NMR(CDCl₃) δ m/z 621.3 1H), 8.35 (d, J = 5.4 Hz, 172.64, 168.72, ([M + H]⁺)1H), 7.35-7.27 (m, 2H), 162.23, 159.43, 7.25-7.20 (m, 2H), 7.01 (d, J =5.5 Hz, 159.35, 158.78, 1H), 6.99-6.88 (m, 146.89, 141.35, 4H), 6.82(dd, J = 8.7, 1.0 Hz, 137.04, 129.69, 2H), 5.11 (dq, J = 9.1, 6.4 Hz,129.39, 121.19, 1H), 4.61 (ddd, J = 10.9, 8.2, 120.61, 115.42, 7.0 Hz,1H), 4.48 (s, 2H), 114.46, 109.87, 81.18, 4.28 (t, J = 8.7 Hz, 1H), 3.95(t, J = 6.0 Hz, 74.77, 67.87, 67.37, 2H), 3.90 (s, 3H), 66.05, 56.31,51.63, 3.73 (q, J = 7.0 Hz, 2H), 2.37 (dt, J = 12.9, 40.21, 33.75,30.54, 6.6 Hz, 1H), 2.07 (td, J = 9.0, 28.48, 19.29, 18.32, 7.1, 3.6 Hz,2H), 15.08 1.96-1.82 (m, 1H), 1.82-1.62 (m, 3H), 1.44-1.34 (m, 1H),1.33-1.26 (m, 6H), 1.26-1.18 (m, 1H) F186 — — ESIMS ¹H NMR (CDCl₃) δ8.53 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 559.3 1H), 8.35 (d, J = 5.4Hz, 172.64, 168.72, ([M + H]⁺) 1H), 7.33-7.27 (m, 2H), 162.21, 159.46,7.01 (d, J = 5.5 Hz, 1H), 146.88, 141.37, 6.94 (dd, J = 8.0, 3.2 Hz,3H), 129.62, 121.06, 5.15-5.00 (m, 1H), 4.60 (dt, J = 10.8, 115.39,109.86, 81.14, 7.1 Hz, 1H), 4.48 (s, 2H), 74.82, 70.81, 67.86, 4.23 (t,J = 8.8 Hz, 1H), 67.36, 58.44, 56.30, 3.90 (s, 3H), 3.73 (q, J = 7.0 Hz,51.61, 40.12, 33.79, 2H), 3.37 (t, J = 6.6 Hz, 2H), 30.57, 28.17, 19.16,3.26 (s, 3H), 2.37 (dt, J = 13.0, 18.33, 15.07 6.7 Hz, 1H), 1.98-1.76(m, 3H), 1.76-1.61 (m, 2H), 1.56-1.42 (m, 1H), 1.42-1.32 (m, 1H), 1.29(dt, J = 7.0, 3.8 Hz, 6H), 1.18 (dd, J = 15.2, 7.5 Hz, 1H) F187 — —HRMS-ESI ¹H NMR (CDCl₃) δ 8.35 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z)1H), 8.27 (d, J = 5.4 Hz, 172.76, 170.02, [M + Na]⁺ 1H), 6.96 (d, J =5.5 Hz, 162.86, 160.13, calcd for 1H), 5.82 (s, 2H), 4.88 (dq, J = 9.0,145.79, 143.82, C₂₈H₄₄O₁₀N₂Na, 6.4 Hz, 1H), 4.56 (dt, J = 10.8, 142.27,109.70, 89.47, 591.2888; 7.1 Hz, 1H), 4.10 (s, 2H), 84.00, 80.30, 75.35,found, 3.90 (s, 3H), 3.59 (q, J = 7.0 Hz, 71.21, 67.75, 67.13, 591.29142H), 3.42 (q, J = 7.8, 7.2 Hz, 58.46, 56.21, 51.83, 3H), 3.32 (s, 3H),40.21, 33.57, 30.37, 3.29 (dd, J = 8.1, 6.1 Hz, 1H), 29.13, 28.33,19.48, 3.05 (t, J = 8.8 Hz, 1H), 2.34 (dt, J = 13.2, 19.40, 19.08,18.12, 6.5 Hz, 1H), 1.97 (dtd, 14.99 J = 10.8, 7.5, 3.2 Hz, 1H), 1.85(dp, J = 13.2, 6.6 Hz, 1H), 1.67 (ddt, J = 27.8, 14.0, 6.7 Hz, 3H),1.59-1.44 (m, 2H), 1.41 (d, J = 6.4 Hz, 3H), 1.33 (q, J = 11.3 Hz, 1H),1.23 (t, J = 7.0 Hz, 3H), 1.10-1.00 (m, 1H), 0.92 (dd, J = 6.7, 2.5 Hz,6H) F188 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.52 (d, J = 8.2 Hz, ¹³C NMR(CDCl₃) δ (m/z) 1H), 8.34 (d, J = 5.4 Hz, 172.70, 168.72, [M + Na]⁺ 1H),7.00 (d, J = 5.5 Hz, 162.18, 159.41, calcd for 1H), 4.94-4.82 (m, 1H),146.88, 141.42, C₂₇H₄₂O₉N₂Na, 4.54 (ddd, J = 10.8, 8.2, 7.0 Hz, 137.00,109.82, 84.04, 561.2783; 1H), 4.48 (s, 2H), 3.90 (s, 3H), 80.33, 75.38,71.28, found, 3.73 (q, J = 7.0 Hz, 2H), 67.86, 67.36, 58.51, 561.28023.41 (q, J = 7.4, 6.6 Hz, 3H), 56.30, 51.58, 40.25, 3.32 (s, 3H),3.32-3.26 (m, 1H), 33.82, 30.42, 29.17, 3.03 (t, J = 8.8 Hz, 1H), 28.36,19.51, 19.43, 2.31 (dt, J = 13.2, 6.5 Hz, 1H), 19.07, 18.13, 15.08 1.96(dtd, J = 10.6, 7.4, 3.1 Hz, 1H), 1.83 (dq, J = 13.3, 6.6 Hz, 1H),1.75-1.63 (m, 2H), 1.62 (s, 1H), 1.56-1.44 (m, 2H), 1.40 (d, J = 6.4 Hz,3H), 1.29 (m, 4H), 1.03 (dd, J = 13.3, 5.9 Hz, 1H), 0.91 (dd, J = 6.7,2.7 Hz, 6H) F189 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.37 (d, J = 8.0 Hz, ¹³CNMR (CDCl₃) δ (m/z) 1H), 8.28 (d, J = 5.3 Hz, 172.79, 170.07, [M + H]⁺1H), 7.30 (d, J = 7.7 Hz, 162.92, 160.18, calcd for 2H), 6.94 (dd, J =7.1, 4.6 Hz, 159.68, 145.80, C₂₉H₃₉O₉N₉, 4H), 5.83 (s, 2H), 143.95,142.29, 559.2650; 5.16-5.01 (m, 1H), 4.61 (dt, J = 10.8, 7.4 Hz, 129.60,120.95, found, 1H), 4.22 (t, J = 8.8 Hz, 115.40, 109.70, 99.98, 559.26541H), 4.10 (s, 2H), 3.91 (s, 3H), 89.57, 81.44, 74.86, 3.59 (q, J = 7.0Hz, 2H), 67.81, 67.19, 56.23, 2.40 (dt, J = 12.5, 6.4 Hz, 1H), 51.89,44.98, 33.68, 1.95-1.78 (m, 1H), 1.77-1.59 (m 27.05, 23.53, 18.85, 4H),1.38 (q, J = 12.7, 11.9 Hz, 18.38, 15.02, 11.88, 1H), 1.30 (d, J = 6.4Hz, 0.00 3H), 1.27-1.19 (m, 4H), 1.17 (s, 1H), 0.88 (t, J = 7.2 Hz, 3H)F190 — — ESIMS ¹H NMR (CDCl₃) δ 8.29 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δm/z 669 1H), 8.25 (d, J = 5.4 Hz, 172.62, 169.97, [M + H]⁺ 1H), 7.09 (d,J = 7.9 Hz, 162.83, 160.09, 2H), 7.03 (d, J = 8.0 Hz, 2H), 145.73,143.81, 6.93 (d, J = 5.4 Hz, 1H), 142.18, 137.20, 5.80 (s, 2H), 4.89(dq, J = 9.1, 6.4 Hz, 135.41, 129.02, 1H), 4.55 (dt, J = 10.9, 7.4 Hz,128.58, 1H), 4.08 (s, 2H), 3.88 (s, 131.42-122.86 (m), 109.65, 3H), 3.80(dt, J = 8.9, 6.1 Hz, 89.44, 84.20, 74.83, 1H), 3.64-3.54 (m, 3H),71.60, 67.71, 67.10, 3.17 (t, J = 9.0 Hz, 1H), 2.96 (dd, J = 13.3,56.15, 51.69, 45.80, 3.4 Hz, 1H), 36.42, 33.56, 30.73 (q, 2.40-2.13 (m,7H), 1.92-1.76 (m, J = 29.0 Hz), 26.62, 3H), 1.65-1.37 (m, 6H), 23.01(q, J = 3.1 Hz), 1.30-1.14 (m, 4H), 0.93-0.80 (m, 20.93, 18.75, 18.05,1H) 14.94 ¹⁹F NMR (CDCl₃) δ −66.35 F191 — — HRMS-ESI ¹H NMR (CDCl₃) δ8.14 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.07 (d, J = 5.4 Hz,172.74, 170.02, [M + H]⁺ 1H), 6.75 (d, J = 5.5 Hz, 162.87, 160.13, calcdfor 1H), 5.61 (s, 2H), 4.69 (dq, J = 9.0, 145.78, 143.84, C₃₁H₄₇O₁₀N₂,6.4 Hz, 1H), 4.35 (dt, J = 10.7, 142.29, 109.69, 89.49, 607.3225; 7.2Hz, 1H), 3.89 (s, 2H), 84.00, 78.33, 75.41, found, 3.70 (s, 3H), 3.39(q, J = 7.0 Hz, 75.30, 69.06, 67.76, 607.3236 2H), 3.34-3.15 (m, 4H),67.14, 56.21, 51.80, 3.05 (dq, J = 6.5, 3.3 Hz, 2H), 40.47, 33.62,30.66, 2.88 (t, J = 8.9 Hz, 1H), 28.20, 19.02, 18.07, 2.14 (dt, J =13.2, 6.5 Hz, 1H), 14.99, 11.08, 10.64, 1.90-1.72 (m, 1H), 1.48 (dtd, J= 21.5 3.15, 2.99, 2.92, 2.87 11.5, 10.3, 6.2 Hz, 3H), 1.40-1.26 (m,2H), 1.22 (d, J = 6.4 Hz, 3H), 1.13 (q, J = 11.4 Hz, 1H), 1.02 (t, J =7.0 Hz, 3H), 0.85 (dddd, J = 14.8, 6.8, 5.0, 3.5 Hz, 3H), 0.33 (tdd, J =10.0, 4.9, 3.7 Hz, 4H), 0.00 (dtd, J = 10.2, 5.3, 4.7, 2.9 Hz, 4H) F192— — HRMS-ESI ¹H NMR (CDCl₃) δ 8.43 (d, J = 7.5 Hz, ¹³C NMR (CDCl₃) δ(m/z) 1H), 8.27 (dd, J = 5.3, 173.60, 170.02, [M + H]⁺ 3.3 Hz, 1H), 6.96(dd, J = 5.4, 162.79, 160.14, calcd for 1.7 Hz, 1H), 5.82 (d, J = 2.9Hz, 145.80, 143.84, C₂₃H₃₃O₉N₂, 2H), 4.99 (ddt, J = 12.6, 142.28,109.71, 89.47, 481.2181; 9.2, 4.7 Hz, 1H), 86.82, 73.26, 67.74, found,4.61-4.41 (m, 1H), 4.10 (d, J = 2.8 Hz, 67.68, 67.13, 56.21, 481.21832H), 3.90 (d, J = 2.7 Hz, 53.27, 39.67, 36.07, 3H), 3.80 (td, J = 7.5,6.5, 3.2 Hz, 35.73, 32.37, 21.77, 1H), 3.69 (dq, J = 8.8, 5.5, 18.36,14.98 4.7 Hz, 1H), 3.59 (qd, J = 7.0, 2.7 Hz, 2H), 3.42 (tt, J = 6.6,2.9 Hz, 1H), 2.47-2.31 (m, 1H), 2.15-1.82 (m, 3H), 1.75 (t, J = 14.0 Hz,1H), 1.63 (t, J = 13.1 Hz, 1H), 1.57-1.46 (m, 2H), 1.41 (dt, J = 9.7,4.8 Hz, 4H), 1.23 (td, J = 7.0, 3.0 Hz, 3H) F193 70-75 — ESIMS ¹H NMR(CDCl₃) δ 8.29 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ m/z 675 1H), 8.22 (d, J= 5.4 Hz, 172.50, 169.95, ([M + H]⁺) 1H), 7.59 (dd, J = 1.7, 0.8 Hz,162.79, 161.38 (dd, J = 246.4, 1H), 7.15 (dd, J = 3.5, 0.8 Hz, 11.5 Hz),1H), 7.03 (td, J = 8.5, 6.4 Hz, 160.89 (dd, J = 247.5, 1H), 6.92 (d, J =5.4 Hz, 11.6 Hz), 160.05, 1H), 6.73-6.63 (m, 2H), 158.08, 146.84, 6.50(dd, J = 3.5, 1.7 Hz, 1H), 145.65, 143.82, 5.78 (s, 2H), 5.19 (t, J =9.2 Hz, 143.80, 142.02, 1H), 5.09 (dq, J = 9.5, 6.2 Hz 131.50 (dd, J =9.4 6.5 Hz) 1H), 4.59 (dt, J = 10.9, 7.4 Hz, 122.36 (dd, J = 15.7, 1H),4.06 (s, 2H), 3.86 (s, 3H), 111.89, 110.82 (dd, J = 21.0, 3.56 (q, J =7.0 Hz, 2H), 3.6 Hz), 2.70 (dd, J = 13.9, 4.5 Hz, 1H), 109.65, 103.58(t, J = 25.7 Hz), 2.50 (dd, J = 13.9, 10.3 Hz, 56.11, 51.59, 42.51, 1H),2.39-2.29 (m, 1H), 33.28, 29.98, 27.26, 2.18-2.07 (m, 1H), 1.74-1.51 (m,18.66, 17.40, 14.88 3H), 1.30 (d, J = 6.3 Hz, 3H), ¹⁹F NMR (CDCl₃) δ1.28-1.21 (m, 1H), 1.19 (t, J = 7.0 Hz, −112.99 (d, J = 6.8 Hz), 3H),1.11-0.99 (m, −113.49 (d, J = 6.9 Hz) 1H) F194 — — HRMS-ESI ¹H NMR(CDCl₃) δ 8.51 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.33 (d, J =5.4 Hz, 172.72, 169.40, ([M]⁺) 1H), 6.99 (d, J = 5.5 Hz, 162.31, 159.40,calcd for 1H), 4.88 (dq, J = 9.2, 6.4 Hz, 146.75, 141.50, C₃₀H₄₄N₂O₈,1H), 4.54 (ddd, J = 10.8, 8.4, 137.29, 109.75, 84.34, 560.3098; 7.0 Hz,1H), 3.89 (s, 3H), 78.49, 75.34, 67.58, found, 3.81 (t, J = 6.6 Hz, 2H),3.49 (dd, J = 9.6, 58.77, 56.30, 51.57, 560.3112 7.0 Hz, 1H), 3.41 (s,42.30, 37.25, 36.89, 3H), 3.39-3.28 (m, 2H), 34.62, 33.95, 33.92,3.05-2.93 (m, 3H), 2.31 (dt, J = 13.4, 31.83, 27.54, 25.09, 6.8 Hz, 1H),25.06, 18.93, 18.06, 1.91-1.65 (m, 4H), 1.65-1.43 (m, 8H), 11.13, 3.12,2.93 1.40 (d, J = 6.5 Hz, 3H), 1.37-1.23 (m, 1H), 1.15-0.91 (m, 4H),0.61-0.51 (m, 2H), 0.21 (dt, J = 5.8, 4.6 Hz, 2H) F195 — — HRMS-ESI ¹HNMR (CDCl₃) δ 8.47 (d, J = 7.3 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.31 (d,J = 5.4 Hz, 172.61, 169.39, ([M]⁺) 1H), 7.09 (d, J = 8.6 Hz, 162.32,159.40, calcd for 2H), 6.98 (d, J = 5.5 Hz, 1H), 157.82, 146.76,C₃₂H₄₂N₂O₉, 6.83 (d, J = 8.6 Hz, 2H), 141.45, 137.29, 598.2890; 4.91(dq, J = 9.1, 6.4 Hz, 1H), 132.66, 129.73, found, 4.55 (ddd, J = 10.9,8.4, 7.0 Hz, 113.77, 109.78, 83.79, 589.2914 1H), 3.88 (s, 3H), 3.81 (t,J = 6.6 Hz, 78.71, 75.22, 67.58, 2H), 3.78 (s, 3H), 58.78, 56.30, 55.22,3.57 (dd, J = 9.7, 7.0 Hz, 1H), 51.47, 46.17, 35.92, 3.44 (dd, J = 9.7,6.8 Hz, 1H), 34.62, 33.89, 26.55, 3.41 (s, 3H), 3.15 (t, J = 9.0 Hz,18.73, 18.08, 11.18, 1H), 3.07 (dd, J = 13.4, 3.3 Hz, 3.16, 3.00 1H),2.98 (t, J = 6.6 Hz, 2H), 2.35-2.20 (m, 2H), 1.87-1.77 (m, 1H),1.61-1.47 (m, 2H), 1.48-1.37 (m, 1H), 1.45 (d, J = 6.4 Hz, 3H),1.22-1.05 (m, 2H), 0.90-0.79 (m, 1H), 0.63-0.49 (m, 2H), 0.29-0.14 (m,2H) F196 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.50 (d, J = 7.7 Hz, ¹³C NMR(CDCl₃) δ (m/z) 1H), 8.32 (d, J = 5.5 Hz, 172.75, 172.47, [M + H]⁺ 1H),6.98 (d, J = 5.5 Hz, 162.31, 159.44, calcd for 1H), 5.01-4.75 (m, 1H),146.62, 141.81, C₃₀H₄₃O₈N₂, 4.59 (dt, J = 10.6, 7.7 Hz, 1H), 137.40,109.66, 99.97, 559.3014; 3.90 (s, 3H), 3.54-3.37 (m, 4H), 84.00, 78.38,75.48, found, 3.25 (dq, J = 6.6, 3.3 Hz, 2H), 75.26, 69.12, 56.31,559.3016 3.06 (t, J = 8.8 Hz, 1H), 51.46, 40.52, 33.93, 2.34 (dt, J =13.4, 6.5 Hz, 1H), 30.65, 28.15, 18.94, 1.97 (tt, J = 8.2, 4.6 Hz, 2H),18.06, 12.99, 11.09, 1.77-1.60 (m, 3H), 1.57-1.45 (m, 10.66, 9.31, 3.18,3.02, 2H), 1.41 (d, J = 6.4 Hz, 3H), 2.95, 2.88 1.36-1.22 (m, 3H), 1.06(ddt, J = 12.2, 8.6, 4.0 Hz, 5H), 0.60-0.47 (m, 4H), 0.30-0.14 (m, 4H)F197 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.47 (d, J = 8.3 Hz, ¹³C NMR (CDCl₃)δ (m/z) 1H), 8.32 (d, J = 5.4 Hz, 172.64, 169.41, [M + H]⁺ 1H),7.31-7.26 (m, 2H), 162.33, 159.41, calcd for 7.18 (tq, J = 7.4, 1.8 Hz,3H), 146.76, 141.47, C₂₉H₃₉N₂O₈, 6.98 (d, J = 5.4 Hz, 1H), 140.75,137.31, 543.2701; 4.90 (dq, J = 9.2, 6.4 Hz, 1H), 128.87, 128.34, found,4.56 (ddd, J = 10.9, 8.4, 7.0 Hz, 125.89, 109.77, 84.20, 543.2705 1H),3.89 (s, 3H), 75.19, 69.21, 67.59, 3.86-3.75 (m, 3H), 3.63 (dq, J = 8.9,7.0 Hz, 58.79, 56.31, 51.49, 1H), 3.41 (s, 3H), 45.94, 36.91, 34.63,3.22-3.13 (m, 1H), 3.09 (dd, J = 13.3, 33.89, 26.61, 18.75, 3.4 Hz, 1H),2.98 (t, J = 6.6 Hz, 18.02, 15.73 2H), 2.35 (dd, J = 13.3, 11.6 Hz, 1H),2.31-2.21 (m, 1H), 1.89-1.77 (m, 1H), 1.74-1.63 (m, 1H), 1.63-1.51 (m,1H), 1.51-1.38 (m, 1H), 1.45 (d, J = 6.4 Hz, 3H), 1.25 (t, J = 7.0 Hz,3H), 1.22-1.12 (m, 1H), 0.92-0.79 (m, 1H) F198 — — HRMS-ESI ¹H NMR(CDCl₃) δ 8.47 (d, J = 8.0 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 8.32 (d, J =5.4 Hz, 172.64, 169.42, [M + H]⁺ 1H), 7.32-7.26 (m, 2H), 162.33, 159.41,calcd for 7.22-7.14 (m, 3H), 6.98 (d, J = 5.5 Hz, 146.75, 141.47,C₃₀H₄₁N₂O₈, 1H), 4.90 (dq, J = 9.2, 140.80, 137.31, 557.2857; 6.4 Hz,1H), 4.56 (ddd, J = 10.9, 128.87, 128.34, found, 8.4, 7.0 Hz, 1H),125.89, 109.77, 83.99, 557.2869 3.89 (s, 3H), 3.81 (t, J = 6.6 Hz,75.58, 75.24, 67.59, 2H), 3.73 (dt, J = 8.8, 6.5 Hz, 58.79, 56.31,51.49, 1H), 3.52 (dt, J = 8.7, 6.7 Hz, 46.06, 36.83, 34.62, 1H), 3.41(s, 3H), 3.16 (t, J = 9.0 Hz, 33.89, 26.59, 23.60, 1H), 3.13-3.07 (m,18.78, 18.09, 10.75 1H), 2.98 (t, J = 6.6 Hz, 2H), 2.35 (dd, J = 13.3,11.7 Hz, 1H), 2.31-2.22 (m, 1H), 1.84 (ddq, J = 12.1, 7.6, 3.7 Hz, 1H),1.73-1.51 (m, 4H), 1.51-1.36 (m, 1H), 1.45 (d, J = 6.4 Hz, 3H),1.29-1.07 (m, 1H), 0.98 (t, J = 7.4 Hz, 3H), 0.92-0.82 (m, 1H) F199 — —ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 456.3 7.28-7.09 (m, 2H),6.96-6.75 (m, 172.32, 158.69, ([M + Na]⁺) 3H), 5.07 (d, J = 8.3 Hz, 1H),153.90, 128.54, 5.02-4.88 (m, 1H), 119.93, 114.46, 80.59, 4.21-4.02 (m,2H), 2.27-2.07 (m, 78.76, 73.72, 52.00, 1H), 1.81-1.29 (m, 7H), 42.14,35.35, 33.09, 1.36 (s, 9H), 1.29-0.91 (m, 3H), 27.32, 27.21, 26.82, 1.21(d, J = 6.4 Hz, 3H), 26.56, 22.02, 21.02, 0.82-0.73 (m, 1H), 0.72 (d, J= 6.6 Hz, 17.83, 17.39 3H), 0.71 (d, J = 6.7 Hz, 3H) F200 — — ESIMS ¹HNMR (CDCl₃) δ 5.06 (d, J = 8.3 Hz, ¹³C NMR (CDCl₃) δ m/z 436.4 1H),4.90-4.75 (m, 173.40, 154.93, 84.31, ([M + Na]⁺) 1H), 4.21-4.07 (m, 1H),80.43, 79.76, 75.36, 3.44 (dd, J = 8.4, 6.3 Hz, 1H), 52.97, 43.48,36.53, 3.25 (dd, J = 8.4, 6.5 Hz, 1H), 34.21, 29.18, 28.33, 2.97 (t, J =8.9 Hz, 1H), 28.10, 27.99, 27.55, 2.28-2.11 (m, 1H), 1.83 (hept, J = 6.6Hz, 22.98, 22.27, 19.52, 1H), 1.75-1.41 (m, 8H), 19.46, 18.76, 18.191.44 (s, 9H), 1.39 (d, J = 6.4 Hz, 3H), 1.30-1.01 (m, 3H), 0.92 (d, J =6.7 Hz, 3H), 0.91 (d, J = 6.7 Hz, 3H), 0.88 (d, J = 6.6 Hz, 3H), 0.87(d, J = 6.6 Hz, 3H) F201 — — ESIMS ¹H NMR (CDCl₃) δ 5.08 (d, J = 8.1 Hz,¹³C NMR (CDCl₃) δ m/z 434.4 1H), 4.86-4.68 (m, 173.35, 154.95, 84.37,([M + Na]⁺) 1H), 4.14-4.01 (m, 1H), 79.69, 78.61, 75.28, 3.43 (dd, J =9.6, 7.0 Hz, 1H), 52.97, 43.55, 36.43, 3.29 (dd, J = 9.7, 6.9 Hz, 1H),34.16, 28.35, 28.05, 2.93 (t, J = 9.0 Hz, 1H), 27.38, 23.05, 22.22,2.20-2.04 (m, 1H), 1.71-1.37 (m, 7H), 18.68, 18.14, 11.15, 1.37 (s, 9H),1.34 (d, J = 6.5 Hz, 3.10, 3.03 3H), 1.25-0.92 (m, 5H), 0.82 (d, J = 6.6Hz, 3H), 0.81 (d, J = 6.7 Hz, 3H), 0.53-0.43 (m, 2H), 0.20-0.09 (m, 2H)F202 — (Neat) ESIMS ¹H NMR (CDCl₃) δ — 2955, m/z 466.4 5.02-4.69 (m,3H), 4.62-4.46 (m, 1750, ([M + Na]⁺) 0.5H), 4.25-4.10 (m, 0.5H), 1708,3.70-3.55 (m, 1H), 1455, 3.49-3.40 (m, 1H), 3.40-3.28 (m, 1367, 3H),3.07-2.93 (m, 1H), 1296, 2.18-1.98 (m, 1H), 1.81-1.42 (m, 1176, 17H),1.40 (d, J = 6.4 Hz, 3H), 1083 1.35-1.01 (m, 4H), 0.93 (t, J = 7.5 Hz,3H), 0.91-0.83 (m, 7H) F203 87-89 — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR(CDCl₃) δ m/z 534.4 5.02-4.69 (m, 3H), 4.62-4.45 (m, −66.42-−66.63 (m,3F) ([M + Na]⁺) 0.5H), 4.27-4.09 (m, 0.5H), 3.82-3.65 (m, 1H), 3.61-3.47(m, 1H), 3.42-3.26 (m, 3H), 3.09-2.93 (m, 1H), 2.31-1.95 (m, 3H),1.92-1.42 (m, 17H), 1.39 (d, J = 6.4 Hz, 3H), 1.33-1.00 (m, 4H),1.00-0.81 (m, 7H) F204 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2932, (m/z)5.03-4.66 (m, 3H), 4.61-4.46 (m, 1765, ([M]⁺) 0.5H), 4.24-4.09 (m,0.5H), 1707, calcd for 4.08-3.96 (m, 1H), 1454, C₂₆H₄₇NO₆, 3.42-3.27 (m,3H), 3.17-3.04 (m, 1367, 469.3403; 1H), 2.23-1.99 (m, 1H), 1296, found,1.86-0.99 (m, 30H), 1173, 469.3416 0.95-0.83 (m, 7H) 1083 F205 — (Neat)HRMS-ESI ¹H NMR (CDCl₃) δ — 2934, (m/z) 4.97-4.70 (m, 3H), 4.60-4.47 (m,1747, ([M]⁺) 0.5H), 4.25-4.11 (m, 0.5H), 1705, calcd for 3.49 (s, 3H),3.40-3.28 (m, 1454, C₂₂H₄₁NO₆, 3H), 2.97-2.86 (m, 1H), 1366, 415.2934;2.17-2.01 (m, 1H), 1.79-1.42 (m, 1296, found, 16H), 1.42 (d, J = 6.4 Hz,3H), 1170, 415.2943 1.31-1.07 (m, 3H), 1080 0.99-0.82 (m, 7H) F206 —(Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2955, (m/z) 5.02-4.75 (m, 4H),4.66-4.47 (m, 1735, ([M]⁺) 0.5H), 4.32-4.14 (m, 0.5H), 1705, calcd for3.45-3.24 (m, 3H), 1454, C₂₇H₄₇NO₇, 2.85-2.65 (m, 1H), 2.22-1.36 (m,1367, 497.3353; 25H), 1.35-0.94 (m, 7H), 1298, found, 0.93-0.76 (m, 6H)1170 497.3368 F207 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ2937, (m/z) 7.20-7.05 (m, 2H), 7.03-6.87 (m, 173.20, 170.99, 1748,([M]⁺) 2H), 5.14 (d, J = 8.3 Hz, 1H), 161.24 (d, J = 243.7 Hz), 1714,calcd for 4.95-4.79 (m, 1H), 154.90, 136.32 (d, J = 3.2 Hz), 1509,C₂₅H₃₆FNO₅, 4.23-4.06 (m, 1H), 3.56 (dd, J = 9.7, 130.11 (d, J = 7.7Hz), 1367, 449.2578; 7.0 Hz, 1H), 3.43 (dd, J = 9.7, 115.07 (d, J = 21.0Hz), 1220, found, 6.8 Hz, 1H), 3.13-3.04 (m, 83.70, 79.67, 1160 449.25861H), 2.31 (dd, J = 13.4, 11.6 Hz, 78.68, 75.01, 60.30, 1H), 2.23-2.09(m, 1H), 52.87, 46.08, 36.00, 1.86-1.72 (m, 1H), 33.98, 28.27, 26.62,1.61-1.31 (m, 5H), 1.45 (d, J = 6.5 Hz, 20.95, 18.66, 18.07, 3H), 1.43(s, 9H), 14.16, 11.15, 3.12, 1.19-0.99 (m, 1H), 0.89-0.75 (m, 2.97 1H),0.62-0.52 (m, 2H), ¹⁹F NMR (CDCl₃) δ −117.40 0.29-0.20 (m, 2H) F20875-77 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ 2936, (m/z)7.36-7.26 (m, 2H), 7.12-6.86 (m, 173.26, 161.31 (d, J = 243.8 Hz), 1714,([M]⁺) 7H), 5.17-4.96 (m, 2H), 159.56, 1509, calcd for 4.30 (t, J = 8.9Hz, 1H), 154.89, 135.84 (d, J = 2.5 Hz), 1368, C₂₇H₃₄FNO₅, 4.26-4.16 (m,1H), 2.95 (dd, J = 13.7, 3.5 Hz, 130.09 (d, J = 7.8 Hz), 1163 471.2421;1H), 2.38-2.15 (m, 2H), 129.72, found, 2.09-1.95 (m, 1H), 121.26,115.47, 471.2430 1.67-1.45 (m, 3H), 1.44 (s, 9H), 115.11 (d, J = 21.1Hz), 1.33 (d, J = 6.5 Hz, 3H), 81.00, 79.93, 74.53, 1.18-0.90 (m, 2H)52.94, 45.66, 36.09, 34.08, 28.33, 26.83, 18.83, 18.38 ¹⁹F NMR (CDCl₃) δ−117.34 F209 — — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ −117.36, m/z502.3 7.18-7.04 (m, 2H), 7.01-6.88 (m, −117.46 ([M + Na]⁺) 2H), 5.94(ddt, J = 17.3, 10.7, 5.5 Hz, 1H), 5.39-5.27 (m, 1H), 5.19 (dd, J =10.4, 1.7 Hz, 1H), 4.96-4.72 (m, 3H), 4.63-4.48 (m, 0.5H), 4.28 (dd, J =12.4, 5.3 Hz, 1H), 4.25-4.16 (m, 0.5H), 4.13-4.03 (m, 1H), 3.39-3.14 (m,3H), 3.05 (dd, J = 13.3, 3.4 Hz, 1H), 2.33 (dd, J = 13.4, 11.6 Hz, 1H),2.19-1.97 (m, 1H), 1.88-1.72 (m, 1H), 1.73-1.33 (m, 17H), 0.93-0.77 (m,1H) F210 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2936, (m/z) 7.18-7.05 (m,2H), 7.03-6.88 (m, 1746, ([M]⁺) 2H), 4.98-4.68 (m, 3H), 1701, calcd for4.63-4.49 (m, 0.5H), 1509, C₂₆H₄₀FNO₆, 4.27-4.15 (m, 0.5H), 3.80-3.63(m, 1366, 481.2840; 1H), 3.57-3.43 (m, 1H), 1297, found, 3.39-3.23 (m,2H), 3.20-3.08 (m, 1177 481.2842 1H), 3.05 (dt, J = 13.5, 3.5 Hz, 1H),2.98-2.86 (m, 1H), 2.32 (t, J = 12.5 Hz, 1H), 2.17-2.00 (m, 1H),1.94-1.32 (m, 19H), 0.97 (t, J = 7.4 Hz, 3H), 0.91-0.76 (m, 1H) F211 —(Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2957, (m/z) 7.17-7.03 (m, 2H),7.02-6.87 (m, 1748, ([M]⁺) 2H), 5.03-4.66 (m, 2H), 1705, calcd for4.65-4.49 (m, 0.5H), 1509, C₂₇H₄₂FNO₆, 4.29-4.13 (m, 0.5H), 3.61-3.48(m, 1367, 495.2996; 1H), 3.39-3.23 (m, 3H), 1296, found, 3.19-2.99 (m,2H), 2.97-2.87 (m, 1175 495.2993 1H), 2.39-2.24 (m, 1H), 2.21-1.22 (m,20H), 1.08-0.75 (m, 7H) F212 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ ¹⁹F NMR(CDCl₃) δ −117.16, 2978, (m/z) 7.16-7.04 (m, 2H), 7.02-6.89 (m, −117.27,2938, ([M]⁺) 2H), 5.86 (tt, J = 55.1, 4.0 Hz, −125.28-−125.61 (m, 1747,calcd for 1H), 4.95-4.71 (m, 3H), 2F) 1700, C₂₅H₃₆F₃NO₆, 4.60-4.46 (m,0.5H), 1509, 503.2495; 4.25-4.13 (m, 0.5H), 4.04-3.89 (m, 1368, found,1H), 3.84-3.69 (m, 1H), 1297, 503.2499 3.37-3.18 (m, 3H), 3.03 (dd, J =13.3, 1080 3.5 Hz, 1H), 2.41-2.30 (m, 1H), 2.19-1.99 (m, 1H), 1.88-1.75(m, 1H), 1.72-1.32 (m, 17H), 0.93-0.75 (m, 1H) F213 — (Neat) HRMS-ESI ¹HNMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ −117.05, 2954, (m/z) 7.11-7.01 (m, 2H),7.01-6.91 (m, −117.18 1734, ([M]⁺) 2H), 5.11-4.73 (m, 4H), 1703, calcdfor 4.66-4.50 (m, 0.5H), 1509, C₂₉H₄₂FNO₇, 4.33-4.18 (m, 0.5H),3.41-3.24 (m, 1368, 535.2945; 3H), 2.85-2.68 (m, 2H), 1297, found,2.68-2.58 (m, 1H), 2.36 (dd, J = 13.7, 1167 535.2961 11.1 Hz, 1H),2.22-2.02 (m, 1H), 2.01-1.37 (m, 21H), 1.34-1.20 (m, 3H), 1.03-0.88 (m,1H) F214 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ −117.05,2976, (m/z) 7.13-7.01 (m, 2H), 7.02-6.89 (m, −117.17 1737, ([M]⁺) 2H),5.09-4.74 (m, 4H), 1704, calcd for 4.64-4.52 (m, 0.5H), 1510,C₂₇H₄₀FNO₇, 4.34-4.19 (m, 0.5H), 3.42-3.22 (m, 1367, 509.2789; 3H),2.71-2.49 (m, 2H), 1297, found, 2.36 (dd, J = 13.8, 11.2 Hz, 1H), 1177509.2795 2.23-2.01 (m, 1H), 1.98-1.82 (m, 1H), 1.78-1.37 (m, 14H),1.35-1.13 (m, 8H), 1.03-0.85 (m, 1H) F215 — — HRMS-ESI ¹H NMR (CDCl₃) δ7.30 (dd, J = 8.7, ¹³C NMR (CDCl₃) δ (m/z) 7.3 Hz, 2H), 7.00 (td, J =6.3, 173.29, 159.66, ([M]⁺) 3.0 Hz, 4H), 6.96 (t, J = 7.3 Hz, 157.83,154.89, calcd for 2H), 6.79 (d, J = 8.6 Hz, 132.21, 129.67, C₂₈H₃₇NO₆,2H), 5.15-4.99 (m, 2H), 121.17, 115.54, 483.2621; 4.30 (t, J = 9.0 Hz,1H), 113.72, 81.13, 79.90, found, 4.26-4.14 (m, 1H), 3.76 (s, 3H),74.60, 55.20, 52.94, 483.2600 2.93 (dd, J = 13.5, 3.3 Hz, 45.73, 35.93,34.14, 1H), 2.28 (dd, J = 13.5, 11.8 Hz, 28.32, 26.72, 18.80, 1H),2.23-2.16 (m, 1H), 18.40 2.00 (dt, J = 8.3, 3.9 Hz, 1H), 1.64-1.48 (m,2H), 1.43 (s, 9H), 1.33 (d, J = 6.5 Hz, 3H), 1.15-1.02 (m, 1H),1.00-0.87 (m, 1H) F216 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ — Film) (m/z)7.32-7.27 (m, 2H), 6.97-6.90 (m, 2943, ([M]⁺) 3H), 5.14-4.95 (m, 2H),2868, calcd for 4.24-4.10 (m, 2H), 2.27 (dt, J = 13.6, 1743, C₂₆H₃₉NO₅,6.9 Hz, 1H), 1706, 445.2828; 1.88-1.73 (m, 3H), 1.74-1.58 (m, 4H), 1492,found, 1.55-1.46 (m, 4H), 1.44 (s, 1366, 445.2845 9H), 1.41-1.34 (m,2H), 1200, 1.28 (d, J = 6.5 Hz, 3H), 1160 1.24-1.10 (m, 1H), 1.12-0.80(m, 3H) F217 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 5707.07-6.97 (m, 2H), 6.86-6.76 (m, 176.26, 173.56, ([M + Na]⁺) 2H),5.06-4.85 (m, 3H), 157.94, 155.49, 4.77 (d, J = 11.6 Hz, 1H), 3.78 (s,131.94, 129.59, 3H), 3.38-3.26 (m, 3H), 113.80, 81.21, 75.54, 2.74 (p, J= 8.0 Hz, 1H), 2.61 (dd, J = 13.7, 72.72, 58.52, 55.43, 3.7 Hz, 1H),2.31 (dd, 55.22, 44.32, 44.04, J = 13.7, 11.1 Hz, 1H), 35.77, 30.09,30.00, 2.20-2.02 (m, 1H), 1.99-1.52 (m, 29.58, 28.20, 26.48, 12H),1.51-1.40 (m, 9H), 25.72, 25.70, 19.09, 1.27 (d, J = 5.8 Hz, 3H), 17.561.15-1.04 (m, 1H), 1.00 (t, J = 7.5 Hz, 1H), 0.97-0.87 (m, 1H) F218 — —ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ −89.52, m/z 566 7.10-7.00 (m,2H), 6.88-6.76 (m, −89.56 (d, J = 72.5 Hz) ([M + Na]⁺) 2H), 4.97-4.82(m, 2H), 4.81-4.71 (m, 1H), 4.55 (s, 1H), 4.19 (t, J = 9.6 Hz, 1H),3.97-3.84 (m, 1H), 3.78 (s, 3H), 3.72 (dt, J = 9.1, 6.8 Hz, 1H),3.37-3.26 (m, 3H), 3.14 (td, J = 8.9, 3.2 Hz, 1H), 2.97 (dd, J = 13.4,3.5 Hz, 1H), 2.37-2.24 (m, 1H), 2.26-2.02 (m, 3H), 1.81-1.57 (m, 5H),1.58-1.23 (m, 14H), 0.89-0.77 (m, 1H) F219 — — HRMS-ESI ¹H NMR (CDCl₃) δ5.05 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ (m/z) 1H), 4.94-4.77 (m, 173.37,154.92, 84.35, ([M]⁺) 1H), 4.14 (q, J = 8.1 Hz, 1H), 79.79, 78.53,75.28, calcd for 3.48 (dd, J = 9.6, 7.0 Hz, 1H), 52.97, 42.26, 37.26,C₂₄H₄₁NO₅, 3.34 (dd, J = 9.6, 6.9 Hz, 1H), 36.86, 34.29, 33.95,423.2985; 2.97 (t, J = 8.9 Hz, 1H), 31.82, 28.34, 27.59, found, 2.21(dt, J = 13.6, 7.0 Hz, 1H), 25.10, 25.07, 18.87, 423.2998 1.94-1.64 (m,5H), 1.64-1.47 (m, 18.11, 11.13, 3.14, 9H), 1.43 (s, 9H), 1.40 (d, J =6.4 Hz, 2.94 2H), 1.19-0.98 (m, 4H), 0.91 (dd, J = 15.2, 7.9 Hz, 1H),0.59-0.46 (m, 2H), 0.26-0.08 (m, 2H) F220 — — HRMS-ESI ¹H NMR (CDCl₃) δ7.07 (dd, J = 8.7, ¹³C NMR (CDCl₃) δ (m/z) 3.3 Hz, 2H), 173.39, 157.80,([M]⁺) 6.86-6.77 (m, 2H), 4.92-4.73 (m, 2H), 132.82, 129.69, calcd for4.23-4.11 (m, 1H), 113.73, 83.74, 80.58, C₂₈H₄₅NO₇, 3.81-3.76 (m, 3H),3.54 (ddd, J = 8.5, 55.25, 46.32, 46.28, 507.3196; 6.3, 2.3 Hz, 1H),35.76, 30.07, 29.26, found, 3.36-3.25 (m, 3H), 3.10 (td, J = 9.2, 28.38,28.32, 28.25, 507.3173 3.1 Hz, 1H), 3.03 (dt, J = 13.4, 28.19, 26.54,19.56, 3.6 Hz, 1H), 2.91 (s, 1H), 19.50, 19.25, 19.12, 2.33-2.20 (m,1H), 1.89 (dp, J = 13.3, 18.26, 18.18 6.8 Hz, 1H), 1.77 (s, 1H),1.67-1.47 (m, 3H), 1.47-1.37 (m, 15H), 0.96 (t, J = 6.3 Hz, 6H),0.85-0.76 (m, 1H) F221 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ(m/z) 7.12-7.03 (m, 2H), 6.86-6.77 (m, 173.30, 157.80, ([M]⁺) 2H),4.89-4.73 (m, 3H), 132.75, 129.69, calcd for 4.28-4.11 (m, 1H), 3.78 (s,3H), 113.73, 99.98, 88.37, C₂₇H₄₃NO₇, 3.71 (dtd, J = 8.4, 6.6, 1.8 Hz,84.02, 83.98, 83.86, 493.3040; 1H), 3.50 (dtd, J = 8.5, 6.7, 1.7 Hz,81.11, 75.59, 75.52, found, 1H), 3.30 (d, J = 14.0 Hz, 55.25, 46.20,46.12, 493.3018 3H), 3.12 (td, J = 8.9, 3.7 Hz, 35.86, 35.82, 28.32,1H), 3.02 (dd, J = 13.4, 3.3 Hz, 28.23, 26.56, 23.59, 1H), 2.27 (ddd, J= 13.3, 19.21, 18.68, 18.18, 11.7, 6.2 Hz, 1H), 1.76 (s, 1H), 18.12,10.75 1.71-1.50 (m, 5H), 1.44 (dd, J = 10.8, 4.6 Hz, 14H), 0.97 (dd, J =7.8, 6.9 Hz, 3H), 0.81 (s, 1H) F222 — — ESIMS ¹H NMR (CDCl₃) δ 7.29 (dd,J = 1.8, ¹³C NMR (CDCl₃) δ m/z 446.2 0.9 Hz, 1H), 6.27 (dd, J = 3.1,173.31, 154.91, [(M + Na)⁺] 1.9 Hz, 1H), 6.00 (d, J = 3.2 Hz, 154.68,140.98, 1H), 5.05 (d, J = 8.3 Hz, 110.07, 106.00, 83.49, 1H), 4.87 (dq,J = 9.3, 6.1 Hz, 80.24, 75.08, 52.92, 1H), 4.20-4.09 (m, 1H), 43.13,34.10, 32.07, 3.48 (dd, J = 8.4, 6.5 Hz, 1H), 29.32, 29.19, 28.33, 3.28(dd, J = 8.4, 6.4 Hz, 1H), 26.23, 22.01, 19.47, 3.10 (t, J = 9.0 Hz,1H), 19.46, 18.78, 18.18 2.99 (dd, J = 14.5, 3.5 Hz, 1H), 2.48 (dd, J =14.7, 11.3 Hz, 1H), 2.16 (dt, J = 13.5, 6.8 Hz, 1H), 1.88 (tdd, J =16.7, 9.0, 3.6 Hz, 3H), 1.66 (dt, J = 11.8, 2.8 Hz, 1H), 1.53-1.47 (m,1H), 1.43 (s, 9H), 1.46-1.40 (m, 4H), 1.10 (dt, J = 13.8, 10.8 Hz, 1H),0.93 (d, J = 6.7 Hz, 6H) F223 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃)δ m/z 506 5.03-4.74 (m, 3H), 4.30-4.17 (m, 182.04, 173.67, 36.98, ([M +Na]⁺) 1H), 3.39-3.30 (m, 3H), 36.48, 35.09, 34.30, 2.72-2.51 (m, 1H),2.22-2.04 (m, 33.68, 31.84, 28.24, 1H), 1.88-0.75 (m, 36H) 28.18, 25.04,25.02, 22.53, 19.13, 18.95, 18.84, 18.79, 18.29, 17.51 F224 144-145 —ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 400.2 7.32-7.24 (m, 2H),6.94 (dd, J = 7.8, 173.36, 159.67, [(M + Na)⁺] 6.5 Hz, 3H), 5.05 (m,2H), 154.90, 129.57, 4.20 (dt, J = 10.8, 7.7 Hz, 1H), 120.98, 115.47,82.27, 4.13 (t, J = 8.8 Hz, 1H), 79.86, 74.59, 53.05, 2.27 (dt, J =12.8, 6.2 Hz, 1H), 37.61, 34.14, 32.37, 1.90 (d, J = 7.0 Hz, 1H), 28.33,19.15, 18.31, 1.74-1.53 (m, 4H), 1.44 (s, 9H), 17.74 1.30 (d, J = 6.5Hz, 3H), 1.25-1.17 (m, 1H), 0.99 (d, J = 6.9 Hz, 3H) F225 — — ESIMS ¹HNMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 292.2 7.50-7.04 (m, 5H), 5.06 (d, J= 7.9 Hz, 173.39, 154.94, [(M − tBoc + H)⁺] 1H), 4.90 (m, 1H), 4.70 (d,128.46, 127.81, J = 10.8 Hz, 1H), 4.58 (d, J = 10.8 Hz, 127.73, 85.30,79.81, 1H), 4.16 (m, 1H), 75.57, 75.09, 53.01, 3.19 (t, J = 8.9 Hz, 1H),37.92, 34.22, 32.29, 2.31-2.14 (m, 1H), 1.83-1.67 (m, 28.34, 19.01,18.23, 1H), 1.66-1.58 (m, 3H), 17.77 1.46 (d, J = 6.4 Hz, 3H), 1.44 (s,9H), 1.23-1.08 (m, 2H), 1.06 (d, J = 6.8 Hz, 3H) F226 — — ESIMS ¹H NMR(CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 500.3 7.31-7.26 (m, 2H), 7.23-7.15 (m,171.03, 152.84, ([M + Na]⁺) 3H), 4.80 (dd, J = 10.6, 7.9 Hz, 140.62,128.88, 1H), 4.71 (dq, J = 9.4, 6.3 Hz, 128.47, 126.06, 82.69, 1H), 3.50(t, J = 9.0 Hz, 76.09, 74.83, 57.42, 1H), 3.11 (dd, J = 13.4, 4.6 Hz,47.48, 37.80, 30.66, 1H), 2.47 (dd, J = 13.5, 27.96, 27.34, 19.75, 10.4Hz, 1H), 2.30-2.20 (m, 18.25 1H), 1.98 (dddd, J = 13.1, 7.8, 5.2, 2.2Hz, 1H), 1.76 (ddd, J = 10.1, 8.3, 4.5 Hz, 1H), 1.60 (dd, J = 10.3, 6.5Hz, 2H), 1.54-1.45 (m, 20H), 1.45-1.39 (m, 2H), 1.26 (t, J = 7.1 Hz, 2H)F227 — — ESIMS ¹H NMR (300 MHz, CDCl₃) δ ¹³C NMR (75 MHz, m/z 458.37.31-7.20 (m, 2H), CDCl₃) δ 173.40, ([M + Na]⁺) 7.19-7.07 (m, 3H),5.12-4.98 (m, 155.11, 140.95, 1H), 4.88 (dq, J = 9.0, 6.4 Hz, 129.06,128.50, 1H), 4.20-4.05 (m, 1H), 128.46, 126.06, 84.91, 3.91 (ddd, J =10.0, 5.7, 3.9 Hz, 79.94, 75.12, 72.99, 1H), 3.74-3.62 (m, 1H), 72.34,59.25, 53.09, 3.60-3.48 (m, 2H), 3.37 (s, 3H), 45.97, 36.94, 34.30,3.24-3.05 (m, 3H), 2.31 (dd, 28.52, 26.78, 18.91, J = 13.2, 11.6 Hz,1H), 18.38 2.20-2.05 (m, 1H), 1.92-1.75 (m, 1H), 1.45 (d, J = 6.5 Hz,3H), 1.40 (s, 9H), 1.55-1.30 (m, 2H, overlapping), 1.01 (q, J = 11.6 Hz,1H), 0.84-0.68 (m, 1H) F229 108-110 — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR(CDCl₃) δ m/z 504 7.41-7.26 (m, 5H), 7.07 (d, J = 7.9 Hz, 173.32,154.95, ([M + Na]⁺) 2H), 7.02 (d, J = 8.0 Hz, 137.92, 137.48, 2H), 5.04(d, J = 8.3 Hz, 1H), 135.38, 129.06, 4.94 (dq, J = 9.2, 6.5 Hz, 1H),128.73, 128.56, 4.79 (d, J = 10.8 Hz, 1H), 127.94, 127.77, 84.20, 4.63(d, J = 10.8 Hz, 1H), 4.17 (dt, 79.83, 75.73, 75.03, J = 10.8, 7.5 Hz,1H), 3.35 (t, J = 9.0 Hz, 52.94, 45.88, 36.40, 1H), 3.10 (dd, J = 13.3,34.18, 28.36, 26.68, 3.3 Hz, 1H), 2.32 (dd, J = 13.3, 21.04, 18.76,18.33 11.8 Hz, 1H), 2.30 (s, 3H), 2.22-2.11 (m, 1H), 1.89 (ddt, J =12.1, 8.3, 3.8 Hz, 1H), 1.64-1.33 (m, 15H), 1.04 (qd, J = 10.5, 5.5 Hz,1H), 0.88-0.77 (m, 1H) F230 164-166 — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR(CDCl₃) δ m/z 605 7.41-7.26 (m, 5H), 7.07 (d, J = 8.1 Hz, 171.13,152.83, ([M + Na]⁺) 2H), 7.03 (d, J = 8.0 Hz, 137.98, 137.51, 2H),4.88-4.75 (m, 3H), 135.31, 129.01, 4.61 (d, J = 10.8 Hz, 1H), 3.35 (t, J= 9.1 Hz, 128.77, 128.54, 1H), 3.10 (dd, J = 13.3, 127.89, 127.76,84.14, 3.3 Hz, 1H), 82.64, 75.44, 75.21, 2.40-2.28 (m, 4H), 2.22 (tt, J= 13.5, 7.2 Hz, 57.57, 45.77, 36.43, 1H), 2.02-1.88 (m, 2H), 30.83,27.97, 26.84, 1.64-1.41 (m, 24H), 21.04, 19.67, 18.49 0.96-0.84 (m, 1H)F231 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 454.4 7.34-7.23(m, 2H), 7.23-7.11 (m, 173.26, 154.91, ([M + Na]⁺) 3H), 5.02 (d, J = 8.3Hz, 1H), 140.72, 128.86, 4.88 (dq, J = 9.2, 6.4 Hz, 1H), 128.34, 125.90,83.80, 4.14 (ddt, J = 14.3, 8.9, 7.1 Hz, 79.79, 78.74, 75.13, 1H), 3.57(dd, J = 9.7, 7.0 Hz, 52.87, 45.98, 36.85, 1H), 3.44 (dd, J = 9.7, 6.8Hz, 34.17, 31.59, 28.31, 1H), 3.21-3.08 (m, 2H), 26.62, 25.28, 22.65,2.32 (dd, J = 13.3, 11.7 Hz, 1H), 18.65, 18.12, 14.12, 2.21-2.07 (m,1H), 1.86 (tdd, 11.16, 3.16, 3.00 J = 12.1, 6.7, 2.7 Hz, 1H), 1.66-1.25(m, 18H), 1.17-0.99 (m, 2H), 0.84-0.75 (m, 1H), 0.65-0.53 (m, 2H), 0.24(dtt, J = 4.9, 3.5, 1.8 Hz, 2H) F232 110-114 — ESIMS ¹H NMR (CDCl₃) δ¹³C NMR (CDCl₃) δ m/z 570 7.12-7.03 (m, 4H), 4.82-4.69 (m, 171.12,152.82, ([M + Na]⁺) 2H), 3.52 (dd, J = 8.4, 6.3 Hz, 137.73, 135.23, 1H),3.30 (dd, J = 8.4, 6.5 Hz, 128.98, 128.75, 83.64, 1H), 3.11 (t, J = 9.1Hz, 1H), 82.58, 80.32, 75.37, 3.05 (dd, J = 13.2, 3.2 Hz, 57.55, 46.00,36.25, 1H), 2.36-2.13 (m, 5H), 30.81, 29.26, 27.96, 2.01-1.77 (m, 3H),1.48 (s, 24H), 26.73, 21.02, 19.65, 0.96 (d, J = 6.7 Hz, 3H), 19.56,19.51, 18.36 0.95 (d, J = 6.7 Hz, 3H), 0.91-0.79 (m, 1H) F233 — — ESIMS¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 456.4 7.32-7.23 (m, 2H),7.22-7.12 (m, 173.30, 154.92, ([M + Na]⁺) 3H), 5.01 (d, J = 8.3 Hz, 1H),140.86, 128.84, 4.87 (dq, J = 9.3, 6.4 Hz, 1H), 128.32, 125.87, 83.71,4.24-4.05 (m, 1H), 3.55 (dd, 80.65, 79.81, 75.19, J = 8.4, 6.2 Hz, 1H),3.32 (dd, 52.88, 46.10, 36.70, J = 8.4, 6.5 Hz, 1H), 34.19, 29.70,29.26, 3.17-3.03 (m, 2H), 2.31 (dd, J = 13.2, 28.32, 26.60, 19.54, 11.8Hz, 1H), 2.16 (dt, J = 13.1, 19.49, 18.73, 18.19 6.8 Hz, 1H), 1.95-1.69(m, 3H), 1.61-1.48 (m, 3H), 1.43-1.39 (m, 11H), 0.96 (dd, J = 6.8, 5.1Hz, 6H), 0.90-0.73 (m, 2H) F234 — — ESIMS ¹H NMR (CDCl₃) δ 5.06 (d, J =7.9 Hz, ¹³C NMR (CDCl₃) δ m/z 418.3 1H), 4.91-4.78 (m, 173.34, 99.99,83.94, ([M + H]⁺) 1H), 4.15 (d, J = 11.0 Hz, 1H), 80.39, 75.25, 52.96,3.44 (dd, J = 8.4, 6.6 Hz, 1H), 42.21, 34.10, 32.15, 3.25 (dd, J = 8.3,6.5 Hz, 1H), 29.93, 29.19, 28.33, 3.00 (t, J = 8.7 Hz, 1H), 19.48,18.89, 18.15, 2.57 (ddd, J = 14.3, 9.7, 4.6 Hz, 15.37 1H), 2.42 (ddd, J= 12.8, 9.1, 7.2 Hz, 1H), 2.27-2.15 (m, 1H), 2.09 (s, 3H), 1.93 (d, J =7.0 Hz, 1H), 1.87-1.77 (m, 1H), 1.74-1.59 (m, 3H), 1.54-1.46 (m, 2H),1.44 (s, 9H), 1.40 (d, J = 6.4 Hz, 3H), 1.26-1.10 (m, 1H), 0.95 (s, 1H),0.95-0.89 (m, 6H) F235 — — ESIMS ¹H NMR (CDCl₃) δ 5.07 (d, J = 8.1 Hz,¹³C NMR (CDCl₃) δ m/z 412.3 1H), 4.92-4.78 (m, 173.30, 154.91, 83.83,[(M + Na)⁺] 1H), 4.55 (td, J = 5.6, 3.2 Hz, 83.78, 82.14, 80.21, 1H),4.47-4.37 (m, 1H), 79.82, 75.14, 52.97, 4.15 (dt, J = 10.7, 7.8 Hz, 1H),39.75, 34.06, 31.57, 3.43 (dd, J = 8.4, 6.6 Hz, 1H), 31.37, 29.15,28.69, 3.24 (dd, J = 8.4, 6.4 Hz, 1H), 28.32, 19.44, 19.40, 3.09-2.96(m, 1H), 2.22 (dt, J = 13.4, 19.07, 18.14 6.7 Hz, 1H), 2.10-1.95 (m,1H), 1.83 (dp, J = 13.2, 6.6 Hz, 1H), 1.67 (d, J = 7.9 Hz, 3H),1.64-1.53 (m, 2H), 1.44 (s, 9H), 1.40 (d, J = 6.4 Hz, 3H), 1.17 (q, J =11.6 Hz, 1H), 1.08-0.97 (m, 1H), 0.94-0.88 (m, 6H) F236 86-89 — ESIMS ¹HNMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 468 7.11-7.02 (m, 4H), 5.02 (d, J =8.3 Hz, 173.21, 154.85, ([M + Na]⁺) 1H), 4.94-4.81 (m, 1H), 137.49,135.27, 4.14 (dt, J = 10.9, 7.5 Hz, 1H), 128.97, 128.66, 83.74, 3.56(dd, J = 9.7, 7.0 Hz, 1H), 79.72, 78.68, 75.09, 3.43 (dd, J = 9.7, 6.8Hz, 1H), 52.81, 36.30, 34.13, 3.13 (t, J = 9.1 Hz, 1H), 28.26, 26.50,20.96, 3.08 (dd, J = 13.3, 3.4 Hz, 1H), 18.57, 18.06, 11.11, 2.35-2.23(m, 4H), 2.15 (dt, J = 12.8, 3.10, 2.94 6.7 Hz, 1H), 1.83 (ddd, J =12.1, 8.4, 3.9 Hz, 1H), 1.60-1.34 (m, 15H), 1.18-0.96 (m, 2H), 0.85-0.72(m, 1H), 0.61-0.54 (m, 2H), 0.28-0.20 (m, 2H) F237 — — ESIMS ¹H NMR(CDCl₃) δ ¹³C NMR (75 MHz, m/z 452.0 7.31-7.24 (m, 2H), 7.23-7.12 (m,CDCl₃) δ 171.29, ([M + Na]⁺) 3H), 4.84-4.69 (m, 1H), 153.02, 141.05,3.70 (dt, J = 8.7, 6.6 Hz, 1H), 129.09, 128.60, 3.49 (dt, J = 8.6, 6.7Hz, 1H), 126.29, 126.02, 84.17, 3.21-3.02 (m, 2H), 2.89 (t, J = 7.6 Hz,82.76, 75.54, 75.47, 1H), 2.71 (dd, J = 8.2, 7.0 Hz, 57.79, 46.07,44.69, 1H), 2.34 (dd, J = 13.3, 37.08, 31.02, 29.95, 11.7 Hz, 1H), 2.21(ddt, J = 13.5, 28.17, 27.13, 23.82, 10.6, 7.3 Hz, 1H), 19.91, 18.52,10.97 2.01-1.77 (m, 2H), 1.70-1.53 (m, 4H), 1.48 (s, 18H), 1.44 (d, J =6.4 Hz, 3H), 0.96 (t, J = 7.4 Hz, 3H), 0.92-0.79 (m, 1H) F238 — — ESIMS¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 468.2 7.31-7.23 (m, 2H),7.23-7.12 (m, 171.38, 152.94, ([M − Boc + Na]⁺) 3H), 4.82-4.65 (m, 1H),141.10, 128.59, 4.16-4.06 (m, 1H), 3.30-3.13 (m, 128.57, 128.41, 1H),2.88 (t, J = 7.6 Hz, 1H), 126.21, 125.88, 83.83, 2.75-2.66 (m, 1H),82.67, 82.53, 75.93, 2.37-2.23 (m, 1H), 2.20-2.10 (m, 57.91, 45.36,44.61, 0H), 1.98-1.87 (m, 1H), 39.36, 37.03, 32.98, 1.83-1.66 (m, 4H),1.61-1.53 (m, 32.69, 30.89, 29.84, 2H), 1.48 (s, 9H), 1.44 (d, J = 9.0Hz, 28.06, 23.15, 23.09, 2H), 0.99-0.80 (m, 20.10, 18.68 1H) F239 — —HRMS-ESI ¹H NMR (CDCl₃) δ 7.07 (d, J = 8.6 Hz, ¹³C NMR (CDCl₃) δ (m/z)2H), 6.82 (d, J = 8.6 Hz, 173.28, 157.83, ([M]⁺) 2H), 5.00 (d, J = 8.4Hz, 132.68, 129.72, calcd for 1H), 4.88 (dd, J = 9.1, 6.3 Hz, 113.76,83.81, 79.82, C₂₆H₃₉NO₆, 1H), 4.21-4.08 (m, 1H), 78.76, 75.16, 55.24,461.2777; 3.78 (s, 3H), 3.56 (dd, J = 9.7, 7.0 Hz, 52.88, 46.11, 35.89,found, 1H), 3.43 (dd, J = 9.6, 6.8 Hz, 34.22, 28.32, 26.57, 261.27571H), 3.13 (t, J = 9.1 Hz, 18.64, 18.11, 11.17, 1H), 3.06 (dd, J = 13.4,3.4 Hz, 3.16, 2.99 1H), 2.26 (dd, J = 13.4, 11.7 Hz, 1H), 2.22-2.07 (m,1H), 1.91-1.74 (m, 1H), 1.61-1.34 (m, 15H), 1.20-1.08 (m, 1H), 1.03 (q,J = 11.7 Hz, 1H), 0.98-0.71 (m, 1H), 0.65-0.48 (m, 2H), 0.27-0.15 (m,2H) F240 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 484.37.35-7.12 (m, 4H), 6.93 (p, J = 7.4 Hz, 173.28, 159.34, ([M + H]⁺) 4H),6.86-6.76 (m, 2H), 158.76, 129.68, 5.15-4.98 (m, 2H), 129.39, 121.17,4.33-4.15 (m, 2H), 3.94 (t, J = 6.6 Hz, 120.61, 115.40, 2H), 2.33-2.21(m, 1H), 114.42, 99.98, 81.14, 2.06 (dd, J = 16.4, 4.9 Hz, 74.68, 66.01,53.01, 2H), 1.93 (d, J = 12.6 Hz, 1H), 40.14, 34.11, 30.49, 1.89-1.79(m, 1H), 28.33, 24.93, 19.20, 1.79-1.65 (m, 1H), 1.62 (d, J = 14.8 Hz,18.35 1H), 1.44 (s, 9H), 1.31 (d, J = 6.5 Hz, 3H), 1.19 (dd, J = 25.8,13.7 Hz, 2H) F241 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 476.47.35-7.20 (m, 5H), 7.19-7.13 (m, 173.32, 159.66, ([M + Na]⁺) 1H),7.13-7.07 (m, 2H), 154.93, 140.25, 7.05-6.93 (m, 2H), 5.08 (dt, J = 9.2,136.31, 129.70, 3.4 Hz, 2H), 4.77 (d, J = 2.6 Hz, 128.80, 128.32, 1H),4.37 (qt, J = 5.6, 125.97, 121.22, 3.6 Hz, 1H), 4.31 (t, J = 9.0 Hz,115.54, 81.14, 79.91, 1H), 4.27-4.15 (m, 1H), 74.60, 45.62, 36.87, 3.00(dd, J = 13.3, 3.3 Hz, 34.11, 28.33, 26.76, 1H), 2.33 (dd, J = 13.4,11.8 Hz, 18.83, 18.41 1H), 2.27-2.15 (m, 1H), 2.12-2.01 (m, 1H),1.93-1.78 (m, 1H), 1.43 (s, 9H), 1.34 (d, J = 6.5 Hz, 3H), 1.16-1.04 (m,1H), 1.01-0.84 (m, 1H) F242 — — ESIMS ¹H NMR (CDCl₃) δ 7.27 (t, J = 8.0Hz, ¹³C NMR (CDCl₃) δ m/z 422.3 2H), 6.94 (dd, J = 7.7, 173.28, 159.46,([M + H]⁺) 3.3 Hz, 3H), 5.10 (d, J = 8.1 Hz, 154.90, 129.61, 1H),5.08-4.98 (m, 1H), 121.05, 115.38, 81.12, 4.20 (q, J = 7.9, 6.9 Hz, 2H),79.86, 74.71, 70.79, 3.36 (t, J = 6.5 Hz, 2H), 58.42, 52.99, 40.09, 3.25(s, 3H), 2.27 (dt, J = 13.3, 6.8 Hz, 34.12, 30.53, 28.33, 1H), 1.88(ddt, J = 10.8, 28.15, 19.07, 18.36 6.9, 3.9 Hz, 2H), 1.83-1.71 (m, 1H),1.70-1.61 (m, 1H), 1.60-1.52 (m, 1H), 1.44 (s, 10H), 1.28 (d, J = 6.5Hz, 3H), 1.25-1.16 (m, 1H), 1.16-1.05 (m, 1H) F243 — — ESIMS ¹H NMR(CDCl₃) δ 5.06 (d, J = 8.2 Hz, ¹³C NMR (CDCl₃) δ m/z 402.3 1H), 4.83(dq, J = 12.9, 173.35, 154.92, 84.01, ([M + H]⁺) 6.4 Hz, 1H), 80.35,79.80, 75.29, 4.22-4.08 (m, 1H), 3.45-3.35 (m, 3H), 71.28, 58.50, 52.96,3.31 (s, 3H), 3.31-3.22 (m, 40.24, 34.17, 30.37, 1H), 3.01 (t, J = 8.8Hz, 1H), 29.16, 28.33, 19.51, 2.21 (dt, J = 13.1, 6.4 Hz, 1H), 19.42,18.99, 18.16 1.94 (dtd, J = 11.1, 7.6, 3.4 Hz, 1H), 1.83 (dp, J = 13.3,6.7 Hz, 1H), 1.63 (dd, J = 16.5, 6.0 Hz, 2H), 1.54 (d, J = 7.7 Hz, 1H),1.43 (s, 11H), 1.40 (d, J = 6.4 Hz, 3H), 1.23-1.10 (m, 1H), 1.02-0.94(m, 1H), 0.91 (dd, J = 6.7, 2.7 Hz, 6H) F244 63-68 — ESIMS ¹H NMR(CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 490 7.36-7.26 (m, 2H), 7.06 (d, J = 7.8Hz, 173.24, 159.65, ([M + Na]⁺) 2H), 7.04-6.94 (m, 5H), 154.86, 137.04,5.14-5.02 (m, 2H), 4.31 (t, J = 8.9 Hz, 135.36, 129.63, 1H), 4.21 (dt, J= 11.0, 128.97, 128.62, 7.6 Hz, 1H), 2.97 (dd, J = 13.4, 121.14, 115.52,81.13, 3.2 Hz, 1H), 79.83, 74.56, 52.91, 2.36-2.17 (m, 5H), 2.11-2.00(m, 45.59, 36.35, 34.09, 1H), 1.67-1.41 (m, 12H), 28.29, 26.68, 20.97,1.34 (d, J = 6.5 Hz, 3H), 18.76, 18.37 1.16-1.02 (m, 1H), 1.00-0.86 (m,1H) F245 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2952, (m/z) 7.33-7.21 (m,2H), 6.99-6.84 (m, 1752, [M + H]⁺ 3H), 5.10-4.78 (m, 3H), 1705, calcdfor 4.65-4.51 (m, 0.5H), 1597, C₂₇H₄₃NO₆, 4.30-4.10 (m, 1.5H), 3.42-3.29(m, 1493, 477.3090; 3H), 2.24-2.02 (m, 1H), 1367, found, 1.92-1.33 (m,16H), 1.28 (d, J = 6.4 Hz, 1297, 477.3086 3H), 1.26-0.99 (m, 1174 3H),0.80 (d, J = 6.7 Hz, 3H), 0.79 (d, J = 6.5 Hz, 3H), 0.77-0.69 (m, 1H)F246 — (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ — 2954, (m/z) 5.03-4.66 (m, 4H),4.60-4.47 (m, 1747, [M + H]⁺ 0.5H), 4.40-4.12 (m, 0.5H), 1704, calcd for3.53-3.19 (m, 5H), 1454, C₂₅H₄₇NO₆, 2.19-1.42 (m, 18H), 1.40 (d, J = 6.4Hz, 1366, 457.3403; 3H), 1.31-1.04 (m, 3H), 1296, found, 0.99-0.81 (m,13H) 1174, 457.3417 1143, 1084 F247 ESIMS ¹H NMR (CDCl₃) δ 5.06 (d, J =8.2 Hz, ¹³C NMR (CDCl₃) δ m/z, 372.3 1H), 4.83 (dd, J = 9.2, 173.40,84.22, 80.41, ([M + H]⁺) 6.5 Hz, 1H), 79.77, 75.35, 52.97, 4.25-4.05 (m,1H), 3.41 (dd, J = 8.4, 6.6 Hz, 45.17, 34.26, 29.17, 1H), 3.25 (dd, J =8.3, 6.5 Hz, 28.34, 27.10, 23.22, 1H), 2.98 (t, J = 8.9 Hz, 19.49,19.45, 18.70, 1H), 2.21 (dt, J = 12.4, 6.2 Hz, 18.20, 11.94 1H), 1.83(dp, J = 13.2, 6.7 Hz, 1H), 1.70 (dt, J = 9.7, 4.7 Hz, 2H), 1.51 (dd, J= 15.4, 7.4 Hz, 1H), 1.44 (s, 10H), 1.39 (d, J = 6.4 Hz, 5H), 1.25-1.10(m, 2H), 0.99-0.83 (m, 9H) F248 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR(CDCl₃) δ m/z 502 7.43-7.27 (m, 5H), 7.12-7.03 (m, 173.22, 161.33 (dd, J= 246.9, ([M − H]⁻) 1H), 6.82-6.72 (m, 2H), 12.2 Hz), 5.03 (d, J = 8.3Hz, 1H), 4.95 (dq, J = 9.1, 161.09 (dd, J = 246.2, 6.4 Hz, 1H), 4.80 (d,J = 10.9 Hz, 10.5 Hz), 154.89, 1H), 4.63 (d, J = 10.9 Hz, 137.75, 131.52(dd, J = 9.0, 1H), 4.18 (dt, J = 10.9, 7.5 Hz, 7.0 Hz), 128.50, 1H),3.38 (t, J = 9.0 Hz, 127.89, 127.63, 1H), 3.07-2.96 (m, 1H), 123.13 (dd,J = 15.4, 3.3 Hz), 2.49 (dd, J = 13.5, 11.6 Hz, 1H), 111.02 (dd, J =20.9, 2.19 (dt, J = 13.1, 6.9 Hz, 1H), 3.7 Hz), 1.98-1.85 (m, 1H),104.18-103.18 (m), 83.93, 1.72-1.32 (m, 15H), 1.14-0.99 (m, 79.83,75.36, 74.84, 1H), 0.94-0.82 (m, 1H) 52.87, 44.42, 34.05, 29.26, 28.29,27.17, 18.75, 18.24 ¹⁹F NMR (CDCl₃) δ −113.33 (d, J = 6.7 Hz), −113.62(d, J = 6.7 Hz) F249 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ(m/z) 7.39-7.27 (m, 2H), 7.03-6.82 (m, 173.20, 159.18, [M + Na]⁺ 3H),5.18-4.99 (m, 2H), 154.89, 129.74, calcd for 4.21 (q, J = 8.7 Hz, 2H),3.44 (ddd, 121.33, 115.37, 80.94, C₂₂H₃₂BrNNaO₅, J = 10.0, 7.4, 5.0 Hz,1H), 79.95, 74.57, 53.02, 492.1356; 3.33 (ddd, J = 9.9, 8.4, 6.9 Hz,1H), 41.18, 34.13, 33.95, found, 2.28 (dt, J = 13.0, 6.6 Hz, 1H), 31.54,28.33, 19.13, 492.1352 2.10 (dtd, J = 12.6, 7.9, 4.5 Hz, 18.29 1H),2.05-1.96 (m, 1H), 1.85-1.73 (m, 2H), 1.73-1.61 (m, 1H), 1.44 (s, 10H),1.30 (d, J = 6.5 Hz, 3H), 1.28-1.20 (m, 1H), 1.20-1.09 (m, 1H) F250 — —ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ m/z 392.3 7.38-7.16 (m, 2H),7.00-6.87 (m, 173.34, 159.68, [(M + H)+] 3H), 5.19-4.97 (m, 2H), 154.91,129.58, 4.18 (t, J = 8.8 Hz, 2H), 2.27 (dt, J = 13.1, 120.95, 115.40,81.44, 6.7 Hz, 1H), 79.86, 74.74, 53.00, 1.91-1.77 (m, 1H), 1.70-1.58(m, 44.96, 34.20, 28.34, 3H), 1.58-1.48 (m, 1H), 27.85, 27.03, 26.85,1.44 (s, 9H), 1.28 (d, J = 6.5 Hz, 23.50, 18.74, 18.40, 3H), 1.25-1.14(m, 2H), 17.53, 13.61, 11.86 1.12-1.01 (m, 1H), 0.86 (t, J = 7.3 Hz, 3H)F251 — — ESIMS ¹H NMR (CDCl₃) δ 5.06 (d, J = 8.1 Hz, ¹³C NMR (CDCl₃) δm/z 440.4 1H), 4.84 (dq, J = 12.9, 173.29, 154.90, ([M + H]⁺) 6.4 Hz,1H), 4.14 (dt, J = 10.6, 121.90, 84.01, 79.78, 7.7 Hz, 1H), 78.35,75.44, 75.22, 3.49-3.37 (m, 4H), 3.25 (dt, J = 6.8, 3.2 Hz, 69.10,52.93, 40.47, 2H), 3.04 (t, J = 8.8 Hz, 34.18, 30.66, 28.32, 1H),2.28-2.15 (m, 1H), 18.92, 18.09, 11.08, 1.98 (dtd, J = 10.7, 7.5, 3.1Hz, 10.64, 3.16, 3.00, 2.93, 1H), 1.71-1.55 (m, 3H), 2.87 1.55-1.46 (m,2H), 1.43 (s, 9H), 1.41 (d, J = 6.4 Hz, 3H), 1.23-1.10 (m, 1H), 1.05(dddd, J = 14.9, 10.0, 5.9, 2.4 Hz, 2H), 1.00-0.90 (m, 1H), 0.60-0.45(m, 4H), 0.25-0.15 (m, 4H) F253 — — ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR(CDCl₃) δ m/z 626 7.41-7.27 (m, 5H), 7.09 (td, J = 8.7, 171.04, 161.32(dd, J = 246.7, ([M + Na]⁺) 6.8 Hz, 1H), 6.82-6.71 (m, 12.2 Hz), 2H),4.87-4.76 (m, 2H), 162.52-159.74 (m), 4.61 (d, J = 10.9 Hz, 1H), 3.37(t, J = 9.1 Hz, 152.83, 137.85, 1H), 3.06-2.96 (m, 131.74-131.38 (m),128.50, 1H), 2.50 (dd, J = 13.5, 11.6 Hz, 127.87, 127.65, 1H), 2.31-2.16(m, 1H), 123.51-122.90 (m), 2.03-1.89 (m, 1H), 111.34-110.66 (m), 103.61(t, 1.70-1.39 (m, 26H), 1.02-0.91 (m, J = 25.7 Hz), 83.90, 1H) 82.65,75.04, 75.02, 57.50, 44.32, 30.74, 29.22, 27.95, 27.43, 19.71, 18.43 ¹⁹FNMR (CDCl₃) δ −113.52 (d, J = 6.8 Hz), −113.69 (d, J = 6.5 Hz) F254108-115 — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δ m/z 570 7.41-7.27 (m,5H), 7.07 (td, J = 8.7, −113.13-−113.46 (m), ([M + Na]⁺) 6.4 Hz, 1H),6.82-6.70 (m, −113.58-−113.82 (m) 2H), 5.01-4.85 (m, 2H), 4.80 (d, J =10.9 Hz, 2H), 4.62 (d, J = 10.9 Hz, 1.5H), 4.29-4.15 (m, 0.5H),3.45-3.25 (m, 4H), 3.08-2.91 (m, 1H), 2.50 (t, J = 12.5 Hz, 1H),2.21-2.02 (m, 1H), 2.00-1.86 (m, 1H), 1.78-1.34 (m, 16H), 1.00-0.83 (m,1H) F255 — — ESIMS ¹H NMR (CDCl₃) δ 7.09 (dd, J = 8.0, ¹⁹F NMR (CDCl₃) δ−66.37 m/z 563 3.1 Hz, 2H), 7.03 (dd, J = 8.0, ([M + NH₄]⁺) 3.3 Hz, 2H),4.97-4.66 (m, 3H), 3.78 (dd, J = 9.4, 5.3 Hz, 1H), 3.58 (dt, J = 8.8,6.2 Hz, 1H), 3.30 (d, J = 14.2 Hz, 1H), 3.22-3.07 (m, 1H), 2.99-2.84 (m,3H), 2.70 (dd, J = 8.2, 7.0 Hz, 1H), 2.40-2.12 (m, 6H), 1.93-1.73 (m,4H), 1.73-1.35 (m, 16H), 0.90-0.75 (m, 1H) F256 — — ESIMS ¹H NMR (CDCl₃)δ ¹⁹F NMR (CDCl₃) δ m/z 598 7.36-7.05 (m, 6H), 6.85-6.71 (m,−113.14-−113.49 (m), ([M + H]⁺) 2H), 4.99-4.68 (m, 2H), −113.52-−113.90(m) 4.54 (d, J = 9.0 Hz, 0.5H), 4.24-4.14 (m, 0.5H), 3.77 (q, J = 6.8Hz, 1H), 3.61-3.50 (m, 1H), 3.31 (d, J = 13.4 Hz, 3H), 3.15 (td, J =8.9, 4.1 Hz, 1H), 3.02-2.88 (m, 2H), 2.73 (td, J = 7.5, 4.2 Hz, 2H),2.47 (t, J = 12.5 Hz, 1H), 2.17-2.01 (m, 1H), 2.00-1.77 (m, 3H),1.75-1.34 (m, 14H), 0.95-0.79 (m, 1H) F257 — — ESIMS ¹H NMR (CDCl₃) δ¹³C NMR (CDCl₃) δ m/z 484.3 7.30-7.24 (m, 2H), 6.97-6.90 (m, 173.27,158.83, ([M + Na]⁺) 1H), 6.90-6.85 (m, 2H), 154.90, 129.42, 5.05 (d, J =8.2 Hz, 1H), 120.60, 114.44, 83.91, 4.95-4.79 (m, 1H), 4.28-4.09 (m,79.84, 78.29, 75.17, 1H), 4.00 (td, J = 7.3, 6.4, 2.3 Hz, 66.15, 52.91,40.31, 2H), 3.55-3.35 (m, 2H), 34.15, 30.28, 28.32, 3.10 (t, J = 8.9 Hz,1H), 28.12, 18.95, 18.10, 2.31-2.10 (m, 2H), 1.87-1.75 (m, 11.07, 3.16,2.92 1H), 1.75-1.58 (m, 3H), 1.50 (d, J = 11.8 Hz, 1H), 1.46-1.39 (m,12H), 1.16 (q, J = 11.7 Hz, 1H), 1.11-0.95 (m, 2H), 0.54 (ddd, J = 8.0,5.3, 3.8 Hz, 2H), 0.24-0.16 (m, 2H) F258 — — ESIMS ¹H NMR (CDCl₃) δ 5.16(d, J = 7.5 Hz, ¹³C NMR (CDCl₃) δ m/z 336.2 1H), 4.95 (dq, J = 9.5,174.15, 154.82, 86.81, ([M + Na]⁺) 6.2 Hz, 1H), 4.11 (ddd, J = 12.5,79.86, 73.23, 67.71, 7.9, 5.2 Hz, 1H), 54.40, 39.68, 36.07, 3.80 (ddd, J= 8.6, 7.2, 3.6 Hz, 1H), 35.75, 33.00, 28.34, 3.68 (td, J = 9.0, 5.4 Hz,1H), 21.72, 18.37 3.39 (dd, J = 9.5, 6.5 Hz, 1H), 2.31-2.18 (m, 1H),2.05 (dddd, J = 11.8, 8.7, 5.4, 3.6 Hz, 1H), 1.98-1.79 (m, 2H),1.75-1.64 (m, 1H), 1.64-1.55 (m, 1H), 1.53-1.46 (m, 2H), 1.44 (s, 9H),1.40 (d, J = 6.3 Hz, 3H), 1.24 (ddd, J = 18.0, 11.7, 4.8 Hz, 1H) F259 —— — ¹H NMR (CDCl₃) δ 13 C NMR (CDCl₃) δ 7.34-7.19 (m, 2H), 7.02-6.86 (m,173.35, 159.33, 3H), 5.76 (ddd, J = 17.2, 10.3, 138.51, 129.49, 8.0 Hz,1H), 5.17-5.06 (m, 121.10, 116.18, 2H), 5.03 (d, J = 17.1 Hz, 1H),115.78, 99.98, 80.46, 4.94 (d, J = 10.4 Hz, 1H), 74.39, 53.05, 47.47,4.28 (t, J = 8.8 Hz, 1H), 34.13, 31.07, 28.34, 4.25-4.17 (m, 1H),2.56-2.41 (m, 1H), 19.66, 18.36 2.27 (dt, J = 13.5, 6.6 Hz, 1H), 1.85(td, J = 14.6, 7.1 Hz, 1H), 1.75 (dt, J = 14.8, 7.3 Hz, 1H), 1.65 (s,1H), 1.44 (s, 9H), 1.33 (d, J = 6.4 Hz, 3H), 1.31-1.17 (m, 2H) F26045-48 — ESIMS ¹H NMR (CDCl₃) δ 7.60 (d, J = 1.5 Hz, ¹⁹F NMR (CDCl₃) δm/z 552 1H), 7.17 (d, J = 3.5 Hz, −112.78-−113.23 (m), ([M + H]⁺) 1H),7.09-6.96 (m, 1H), −113.37-−113.71 (m) 6.77-6.63 (m, 2H), 6.52 (dd, J =3.4, 1.7 Hz, 1H), 5.19 (q, J = 8.2, 7.2 Hz, 1H), 5.04 (dq, J = 12.5, 6.5Hz, 1H), 4.90 (t, J = 8.7 Hz, 1H), 4.80 (d, J = 11.5 Hz, 1H), 4.58 (t, J= 9.0 Hz, 0.5H), 4.26 (t, J = 7.8 Hz, 0.5H), 3.32 (d, J = 12.2 Hz, 3H),2.70 (dd, J = 13.9, 4.5 Hz, 1H), 2.52 (dd, J = 13.9, 10.1 Hz, 1H),2.25-2.00 (m, 2H), 1.87-1.52 (m, 4H), 1.45 (s, 9H), 1.30 (d, J = 6.3 Hz,3H), 1.13-0.96 (m, 1H) F261 — — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR (CDCl₃) δm/z 536 7.22-7.05 (m, 1H), 6.84-6.71 (m, −113.49 (d, J = 43.3 Hz), ([M +H]⁺) 2H), 4.83 (dq, J = 34.5, 9.9 Hz, −113.74 (d, J = 31.5 Hz) 3H), 4.56(d, J = 9.0 Hz, 0.5H), 4.20 (dd, J = 12.0, 6.7 Hz, 0.5H), 3.54 (t, J =7.3 Hz, 1H), 3.47-3.37 (m, 0.5H), 3.37-3.25 (m, 3H), 3.20-3.09 (m, 1H),3.03-2.85 (m, 2H), 2.71 (t, J = 7.6 Hz, 0.5H), 2.47 (td, J = 13.1, 12.3,4.8 Hz, 1H), 2.17-1.99 (m, 1H), 1.99-1.76 (m, 1H), 1.74-1.32 (m, 16H),1.04-0.77 (m, 7H) F262 161-163 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.62(bs, ¹³C NMR (CDCl₃) δ 3394, (m/z) 3H), 7.26-7.08 (m, 2H), 170.45,159.55, 2953, [M + H]⁺ 6.94-6.73 (m, 3H), 5.06-4.84 (m, 129.60, 121.07,1747, calcd for 1H), 4.22-3.92 (m, 2H), 115.42, 81.29, 75.78, 1597,C₂₀H₃₂NO₃, 2.64-2.39 (m, 1H), 1.89-0.91 (m, 52.60, 43.19, 36.23, 1492,334.2377; 13H), 0.90-0.59 (m, 7H) 31.23, 28.22, 27.80, 1225 found,27.31, 23.01, 22.02, 334.2382 18.48, 18.33 F263 186-188 (Neat) HRMS-ESI¹H NMR (CDCl₃) δ 8.64 (bs, ¹³C NMR (CDCl₃) δ 3369, (m/z) 3H), 4.94-4.69(m, 1H), 170.38, 84.06, 80.53, 2955, [M + H]⁺ 4.15-3.94 (m, 1H),3.51-3.36 (m, 76.38, 52.45, 43.53, 1746, calcd for 1H), 3.31-3.17 (m,1H), 36.38, 31.27, 29.16, 1642, C₁₈H₃₆NO₃, 3.03-2.88 (m, 1H), 2.64-2.39(m, 28.03, 27.95, 27.23, 1475, 314.2690; 1H), 1.93-1.33 (m, 9H), 22.95,22.23, 19.48, 1225 found, 1.41 (d, J = 6.2 Hz, 3H), 19.43, 18.34, 18.08314.2690 1.33-0.98 (m, 3H), 0.98-0.77 (m, 12H) F264 205-207 (Neat)HRMS-ESI ¹H NMR (CDCl₃) δ 8.63 (bs, ¹³C NMR (CDCl₃) δ 3375, (m/z) 3H),4.91-4.75 (m, 1H), 170.35, 84.09, 78.76, 2953, [M + H]⁺ 4.18-3.91 (m,1H), 3.56-3.30 (m, 76.31, 52.42, 43.57, 1746, calcd for 2H), 3.05-2.91(m, 1H), 43.54, 36.26, 31.27, 1634, C₁₈H₃₄NO₃, 2.61-2.38 (m, 1H),1.85-1.32 (m, 27.98, 27.08, 23.00, 1454, 312.2533; 7H), 1.42 (d, J = 6.3Hz, 3H), 22.16, 18.21, 18.01, 1233, found, 1.32-0.98 (m, 5H), 11.09,3.08, 2.98 1076 312.2532 0.96-0.79 (m, 6H), 0.60-0.50 (m, 2H), 0.26-0.15(m, 2H) F265 200-202 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.67 (bs, ¹³C NMR(CDCl₃) δ 3411, (m/z) 3H), 4.96-4.65 (m, 1H), 170.32, 84.33, 76.49,2955, [M + H]⁺ 4.14-3.90 (m, 1H), 3.69-3.55 (m, 75.55, 52.41, 43.47,2872, calcd for 1H), 3.51-3.37 (m, 1H), 36.37, 31.41, 28.04, 1748,C₁₇H₃₄NO₃, 3.04-2.89 (m, 1H), 2.61-2.41 (m, 27.28, 23.53, 23.01, 1478,300.2533; 1H), 1.85-1.32 (m, 9H), 22.19, 18.32, 18.04, 1209 found, 1.43(t, J = 8.5 Hz, 3H), 10.69 300.2532 1.30-0.98 (m, 4H), 0.93 (t, J = 7.4Hz, 3H), 0.90-0.81 (m, 6H) F266 215-217 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ8.73 (bs, ¹³C NMR (CDCl₃) δ 3369, (m/z) 3H), 4.91-4.77 (m, 1H), 170.41,127.08 (q, J = 277 Hz), 1744, [M + H]⁺ 4.03-3.89 (m, 1H), 3.81-3.63 (m,84.51, 76.13, 1635, calcd for 1H), 3.61-3.48 (m, 1H), 71.66, 52.43,43.44, 1453, C₁₈H₃₃F₃NO₃, 3.04-2.94 (m, 1H), 2.59-2.45 (m, 36.32, 31.17,30.72 (q, 1252 368.2407; 1H), 2.29-2.08 (m, 2H), J = 31 Hz), 28.09,found, 1.87-1.43 (m, 9H), 1.40 (d, J = 6.4 Hz, 27.98, 27.17, 23.01 (q,368.2418 3H), 1.31-0.90 (m, 4H), J = 3.2 Hz), 22.89, 0.90-0.83 (m, 6H)22.08, 18.30, 18.01 ¹⁹F NMR (CDCl₃) δ −66.49 F267 — (Neat) HRMS-ESI ¹HNMR (CDCl₃) δ 8.69 (bs, — 2952, (m/z) 3H), 4.88-4.73 (m, 1H), 1746, [M +H]⁺ 4.11-3.89 (m, 2H), 3.17-2.98 (m, 1453, calcd for 1H), 2.96-2.46 (m,2H), 1208, C₁₉H₃₆NO₃, 1.89-0.96 (m, 21H), 1054 326.2690; 0.95-0.81 (m,6H) found, 326.2687 F268 218-220 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.70(bs, — 2932, (m/z) 3H), 4.91-4.71 (m, 1H) 2874, [M + H]⁺ 4.12-3.91 (m,1H), 3.49 (s, 3H), 1751, calcd for 2.98-2.83 (m, 1H), 1580, C₁₅H₃₀NO₃,2.61-2.40 (m, 1H), 1.88-1.35 (m, 1481, 272.2220; 7H), 1.43 (d, J = 6.4Hz, 3H), 1211 found, 1.30-1.02 (m, 4H), 272.2222 0.95-0.80 (m, 6H) F269— (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.70 (bs, ¹³C NMR (CDCl₃) δ 3404,(m/z) 3H), 5.09-4.90 (m, 1H), 176.09, 170.16, 75.71, 2952, [M + H]⁺4.90-4.76 (m, 1H), 4.15-3.95 (m, 74.41, 52.33, 44.02, 1732, calcd for1H), 2.84-2.65 (m, 2H), 43.59, 41.80, 36.15, 1453, C₂₀H₃₆NO₄, 2.64-2.47(m, 1H), 2.01-1.36 (m, 30.04, 29.94, 29.92, 1383, 354.2639; 14H),1.35-0.91 (m, 7H), 27.90, 25.80, 25.67, 1149 found, 0.91-0.76 (m, 6H)25.66, 22.84, 22.13, 354.2655 18.20, 17.43 F271 222-224 (Neat) HRMS-ESI¹H NMR (CDCl₃) δ 8.54 (bs, ¹⁹F NMR (CDCl₃) δ −117.24 2923, (m/z) 3H),7.14-7.03 (m, 2H), 2877, [M + H]⁺ 7.01-6.89 (m, 2H), 4.91-4.72 (m, 1746,calcd for 1H), 4.11-3.89 (m 1H), 1508, C₂₀H₂₉FNO₃, 3.58-3.48 (m, 1H),3.46-3.35 (m, 1218, 350.2126; 1H), 3.16-2.96 (m, 2H), 1073 found,2.51-2.34 (m, 1H), 2.34-2.18 (m, 350.2130 1H) 1.86-1.68 (m, 1H),1.66-1.24 (m, 4H), 1.39 (d, J = 6.5 Hz, 3H), 1.18-1.01 (m, 1H),0.84-0.68 (m, 1H), 0.65-0.51 (m, 2H), 0.30-0.17 (m, 2H) F272 196-198 —HRMS-ESI ¹H NMR (CDCl₃) δ 8.58 (bs, ¹³C NMR (CDCl₃) δ (m/z) 3H),7.34-7.25 (m, 2H), 170.26, 161.32 (d, J = 244.1 Hz), [M + H]⁺ 7.06-6.86(m, 7H), 5.09-4.92 (m, 159.34, calcd for 1H), 4.32-4.18 (m, 1H), 135.46(d, J = 3.2 Hz), C₂₂H₂₇FNO₃, 4.16-3.97 (m, 1H), 2.97-2.85 (m, 130.03 (d,J = 7.9 Hz), 372.1969; 1H), 2.59-2.41 (m, 1H), 129.79, 121.46, found,2.34-2.21 (m, 1H), 2.07-1.91 (m, 115.38, 115.18 (d, J = 20.9 Hz),372.1979 1H), 1.76-1.37 (m, 4H), 80.66, 75.74, 1.27 (d, J = 6.4 Hz, 3H),52.43, 45.39, 36.01, 1.00-0.81 (m, 1H) 31.13, 26.78, 18.38, 18.21 ¹⁹FNMR (CDCl₃) δ −117.02 F273 210-212 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.56(bs, ¹³C NMR (75 MHz, 3378, (m/z) 3H), 7.15-7.01 (m, 2H), CDCl₃) δ170.33, 2937, [M + H]⁺ 7.01-6.86 (m, 2H), 6.03-5.83 (m, 161.39 (d, J =244.0 Hz), 1743, calcd for 1H), 5.33 (d,J = 17.2 Hz, 1H), 136.02 (d, J =3.1 Hz), 1601, C₁₉H₂₇FNO₃, 5.22 (d, J = 10.4 Hz, 1H), 134.25, 1508,336.1969; 4.92-4.74 (m, 1H), 4.25 (dd, J = 12.1, 130.16 (d, J = 7.5 Hz),1218 found, 5.5 Hz, 1H), 117.36, 115.25 (d, J = 21.1 Hz), 336.19704.16-3.88 (m, 2H), 3.82-3.58 (m, 1H), 83.99, 76.11, 3.24-3.09 (m, 1H),74.89, 52.40, 45.75, 3.09-2.93 (m, 1H), 2.55-2.35 (m, 36.12, 31.17,26.73, 1H), 2.35-2.16 (m, 1H), 18.38, 18.09 1.87-1.70 (m, 1H), 1.70-1.28(m, 6H), 0.89-0.67 (m, 1H) F274 215-217 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ8.64 (bs, — 3385, (m/z) 3H), 7.22-6.74 (m, 4H), 2934, [M + H]⁺ 4.99-4.66(m, 1H), 4.05-3.57 (m, 2876, calcd for 3H), 3.57-3.39 (m, 1H), 1742,C₁₉H₂₉FNO₃, 3.16-2.92 (m, 2H), 2.85-2.67 (m, 1508, 338.2126; 1H),2.57-2.36 (m, 1H), 1215 found, 2.36-2.16 (m, 1H), 1.86-1.25 (m, 338.21268H), 0.97 (t, J = 7.4 Hz, 3H), 0.89-0.63 (m, 1H) F275 163-165 (Neat)HRMS-ESI ¹H NMR (CDCl₃) δ 8.60 (bs, — 2956, (m/z) 3H), 7.24-6.79 (m,4H), 2875, [M + H]⁺ 5.04-4.67 (m, 2H), 4.12-3.84 (m, 1748, calcd for1H), 3.59-3.46 (m, 1H), 1509, C₂₀H₃₁FNO₃, 3.38-3.21 (m, 1H), 3.18-2.93(m, 1221 352.2282; 2H), 2.56-2.36 (m, 1H), found, 2.36-2.17 (m, 1H),1.99-1.80 (m, 352.2282 1H), 1.80-1.29 (m, 7H), 1.05-0.67 (m, 7H) F276204-206 (Neat) HRMS-ESI ¹H NMR (CD₃OD) δ ¹⁹F NMR (CDCl₃) δ −113.38,2942, (m/z) 7.27-7.16 (m, 2H), 7.08-6.96 (m, −121.92 (2F) 2882, [M + H]⁺2H), 5.99 (tt, J = 55.1, 3.7 Hz, 1740, calcd for 1H), 5.02-4.92 (m, 1H),1509, C₁₈H₂₅F₃NO₃, 4.09-3.81 (m, 3H), 3.79-3.57 (m, 1216 360.1781; 1H),3.45-3.38 (m, 1H), found, 3.17-3.06 (m, 1H), 2.45 (dd, J = 13.5,360.1786 11.5 Hz, 1H), 2.29-2.14 (m, 1H), 1.92-1.75 (m, 1H), 1.75-1.57(m, 2H), 1.52 (d, J = 6.4 Hz, 3H), 1.41-1.27 (m, 1H), 0.99-0.81 (m, 1H)F277 200-202 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ 8.63 (bs, ¹⁹F NMR (CDCl₃)δ −116.96 3376, (m/z) 3H), 7.09-7.00 (m, 2H), 2954, [M + H]⁺ 7.00-6.89(m, 2H), 5.06-4.87 (m, 1733, calcd for 2H), 4.14-3.93 (m, 1H), 1635,C₂₂H₃₁FNO₄, 2.81-2.57 (m, 2H), 2.57-2.40 (m, 1509, 392.2232; 1H),2.40-2.25 (m, 1H), 1220 found, 2.03-1.41 (m, 11H), 392.2236 1.38-1.14(m, 5H), 0.99-0.78 (m, 1H) F278 193-195 (Neat) HRMS-ESI ¹H NMR (CDCl₃) δ8.63 (bs, ¹³C NMR (CDCl₃) δ 3375, (m/z) 3H), 7.08-6.99 (m, 2H), 176.43,170.09, 2972, [M + H]⁺ 6.99-6.90 (m, 2H), 5.10-4.82 (m, 161.39 (d, J =244.2 Hz), 1735, calcd for 2H), 4.12-3.91 (m, 1H), 135.23 (d, J = 3.2Hz), 1635, C₂₀H₂₉FNO₄, 2.69-2.38 (m, 3H) 2.31 (dd J = 13.8, 130.02 (d, J= 7.7 Hz), 1509, 366.2075; 11.1 Hz, 1H), 115.27 (d, J = 21.3 Hz), 1219found, 1.99-1.80 (m, 1H), 1.76-1.40 (m, 3H), 75.11, 74.26, 366.20771.33-1.12 (m, 10H), 52.24, 43.84, 35.77, 0.97-0.78 (m, 1H) 34.17, 33.62,26.65, 19.07, 18.97, 18.82, 17.36 ¹⁹F NMR (CDCl₃) δ −116.88 F279 — —ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR (CD₃OD) δ m/z 334.4 7.31-7.22 (m, 2H),7.21-7.13 (m, 171.46, 141.99, ([M + H]⁺) 3H), 3.98-3.83 (m, 1H), 129.89,129.46, 3.77-3.70 (m, 1H), 3.66 (q, J = 5.5, 127.06, 84.74, 81.69, 5.0Hz, 1H), 77.66, 53.00, 47.35, 3.61-3.53 (m, 1H), 3.41 (dd, J = 8.5, 6.4Hz, 37.69, 32.11, 30.51, 1H), 3.23 (t, J = 8.9 Hz, 28.03, 19.88, 19.83,1H), 3.10 (dd, J = 13.3, 3.4 Hz, 19.45, 18.49 1H), 2.47-2.30 (m, 1H),2.20 (qd, J = 8.4, 7.5, 5.0 Hz, 1H), 1.89 (dt, J = 13.2, 6.6 Hz, 1H),1.84-1.74 (m, 1H), 1.64 (dp, J = 8.5, 3.2, 2.8 Hz, 2H), 1.48 (d, J = 6.4Hz, 4H), 1.36-1.24 (m, 2H), 0.98 (dd, J = 6.7, 3.6 Hz, 6H), 0.95-0.79(m, 2H) F280 — — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR (CDCl₃) δ m/z 333.47.33-7.22 (m, 2H), 7.22-7.11 (m, 173.98, 144.51, ([M + H]⁺) 3H), 3.91(dd, J = 10.9, 7.1 Hz, 132.44, 131.98, 1H), 3.66-3.59 (m, 2H), 129.58,87.29, 82.26, 3.51 (dd, J = 9.9, 6.8 Hz, 1H), 80.13, 70.67, 55.51,3.30-3.23 (m, 2H), 3.15 (dd, 49.75, 40.33, 34.61, J = 13.1, 3.3 Hz, 1H),30.63, 21.94, 20.95, 2.39 (dd, J = 13.3, 11.6 Hz, 1H), 14.60, 6.06 2.20(ddt, J = 12.6, 8.6, 4.6 Hz, 1H), 1.80 (ddt, J = 12.0, 7.9, 4.0 Hz, 1H),1.63 (dq, J = 9.5, 5.3, 4.4 Hz, 2H), 1.56-1.40 (m, 4H), 1.40-1.25 (m,1H), 1.12 (dddd, J = 14.9, 6.9, 5.9, 2.7 Hz, 1H), 0.94-0.77 (m, 1H),0.64-0.47 (m, 2H), 0.32-0.17 (m, 2H) F281 — — ESIMS ¹H NMR (CDCl₃) δ8.66 (s, — m/z 354.3 3H), 7.35-7.27 (m, 2H), ([M + H]⁺) 7.25-7.11 (m,3H), 7.07 (d, J = 7.3 Hz, 2H), 7.03-6.93 (m, 3H), 5.04 (s, 1H),4.47-4.34 (m, 1H), 4.29 (s, 1H), 3.77 (dddd, J = 5.9, 4.6, 2.8, 1.8 Hz,1H), 3.68-3.60 (m, 1H), 2.97 (d, J = 12.2 Hz, 1H), 2.31 (t, J = 12.3 Hz,1H), 2.07 (s, 1H), 1.92-1.77 (m, 2H), 1.73-1.36 (m, 4H), 0.96-0.83 (m,1H) F282 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.58 (s, ¹³C NMR (CDCl₃) δ (m/z)3H), 7.29-7.23 (m, 2H), 170.16, 140.43, [M + H]⁺ 7.20-7.09 (m, 3H),4.88-4.76 (m, 128.76, 128.37, calcd for 1H), 4.03-3.91 (m, 1H), 125.96,83.70, 76.33, C₁₉H₃₀NO₃, 3.55-3.43 (m, 1H), 3.16-2.98 (m, 75.68, 52.19,45.95, 320.222; 2H), 2.49-2.38 (m, 1H), 36.74, 31.33, 26.28, found, 2.29(dd, J = 13.2, 11.8 Hz, 1H), 23.58, 18.18, 17.97, 320.2218 1.87-1.73 (m,1H), 10.74 1.70-1.50 (m, 5H), 1.50-1.36 (m, 2H), 1.41 (d, J = 6.5 Hz,3H), 0.97 (t, J = 7.4 Hz, 3H), 0.79-0.69 (m, 1H) F283 — — ESIMS ¹H NMR(CDCl₃) δ 8.57 (s, — m/z 347.4 3H), 7.36-7.20 (m, 2H), ([M + H]⁺)7.20-7.05 (m, 3H), 4.94-4.66 (m, 1H), 4.22-3.89 (m, 2H), 3.37-3.07 (m,2H), 2.87 (t, J = 7.6 Hz, 1H), 2.70 (dd,J = 8.2, 7.0 Hz, 1H), 2.54-2.33(m, 1H), 2.33-2.11 (m, 1H), 1.87-1.64 (m, 7H), 1.43 (br s, 4H), 1.26 (brs, 3H), 0.93-0.70 (m, 1H) F284 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.55 (s,¹³C NMR (CDCl₃) δ (m/z) 3H), 7.29-7.22 (m, 2H), 170.22, 140.40, [M + H]⁺7.20-7.10 (m, 3H), 4.81 (dq, J = 9.4, 128.77, 128.37, calcd for 6.4 Hz,1H), 125.96, 83.92, 76.21, C₁₈H₂₈NO₃, 4.05-3.91 (m, 1H), 3.78 (dq, J =8.8, 6.9 Hz, 69.30, 55.22, 45.84, 306.2064; 1H), 3.59 (dq, J = 8.9, 7.0Hz, 36.83, 31.26, 26.29, found, 1H), 3.15-3.07 (m, 1H) 18.15, 17.89,15.72 306.2062 3.07-3.00 (m, 1H), 2.47-2.37 (m, 1H), 2.35-2.24 (m, 1H),1.84-1.71 (m, 1H), 1.61-1.48 (m, 2H), 1.47-1.35 (m, 2H), 1.40 (d, J =6.5 Hz, 3H), 1.24 (t, J = 6.9 Hz, 3H), 0.79-0.65 (m, 1H) F285 — — ESIMS1H NMR (300 MHz, CD₃OD) 13C NMR (75 MHz, m/z 336.2 δ 7.35-7.22 (m, 2H),7.17 (d, CD3OD) δ 170.26, ([M + H]⁺) J = 7.4 Hz, 3H), 4.84 (d, J = 1.0Hz, 140.88, 128.80, 1H), 3.92 (dt, J = 10.0, 128.26, 125.84, 84.19, 4.8Hz, 2H), 3.74 (dq, J = 10.8, 76.24, 72.70, 72.14, 5.5, 5.0 Hz, 1H), 3.65(s, 66.97, 58.07, 51.86, 3H), 3.55 (t, J = 4.3 Hz, 2H), 45.94, 36.51,30.93, 3.37 (s, 3H), 3.34-3.25 (m, 26.79, 18.27, 17.31 1H), 3.16 (dd, J= 13.2, 3.3 Hz, 1H), 2.38 (t, J = 12.4 Hz, 1H), 2.31-2.17 (m, 1H),1.88-1.73 (m, 1H), 1.72-1.56 (m, 2H), 1.49 (d, J = 6.3 Hz, 4H),1.39-1.24 (m, 1H), 0.91-0.76 (m, 1H) F287 — — HRMS-ESI ¹H NMR (CD₃OD) δ¹³C NMR (CD₃OD) δ (m/z) 7.33 (ddd, J = 9.8, 5.9, 2.2 Hz, 2H), 170.13,159.60, ([M]⁺) 7.14-7.03 (m, 4H), 6.98 (t, J = 7.3 Hz, 158.13, 131.91,calcd for 1H), 6.83 (d, J = 8.6 Hz, 129.39, 129.32, C₂₃H₂₉NO₄, 2H), 5.14(dq, J = 9.7, 6.4 Hz, 120.97, 115.15, 383.2097; 1H), 4.47 (t, J = 8.9Hz, 113.45, 80.41, 75.60, found, 1H), 3.98 (dd, J = 10.9, 7.1 Hz, 54.21,51.63, 45.69, 383.2075 1H), 3.76 (s, 3H), 35.49, 30.78, 26.56, 2.92 (dd,J = 13.5, 3.4 Hz, 1H), 18.02, 17.21 2.37 (dd, J = 13.4, 11.6 Hz, 1H),2.26 (ddd, J = 11.9, 7.4, 4.2 Hz, 1H), 2.03 (ddd, J = 10.5, 7.3, 3.6 Hz,1H), 1.75 (d, J = 9.3 Hz, 2H), 1.62 (tt, J = 13.4, 6.6 Hz, 1H), 1.37 (d,J = 6.4 Hz, 4H), 1.01 (d, J = 14.8 Hz, 1H) F288 — — HRMS-ESI ¹H NMR(CDCl₃) δ 8.76 (s, ¹³C NMR (CDCl₃) δ (m/z) 3H), 7.31-7.22 (m, 2H),170.30, 159.58, ([M]⁺) 6.99-6.84 (m, 3H), 5.03 (p, J = 6.6 Hz, 129.62,121.09, calcd for 1H), 4.26-3.96 (m, 2H), 115.49, 81.25, 76.00,C₂₁H₃₁NO₃, 3.71 (s, 3H), 2.64-2.51 (m, 67.09, 52.45, 42.05, 345.2304;1H), 2.04-1.59 (m, 6H), 37.15, 36.76, 33.63, found, 1.59-1.31 (m, 5H),1.28 (d, J = 6.3 Hz, 31.73, 31.41, 27.29, 345.2287 3H), 1.08-0.88 (m,3H) 25.04, 18.51, 18.32 F289 — (Thin HRMS-ESI ¹H NMR (CDCl₃) δ 8.67 (s,— Film) (m/z) 3H), 6.99 (d, J = 8.2 Hz, 2H), 2946, ([M]⁺) 6.80 (d, J =7.9 Hz, 2H), 2871, calcd for 4.97 (s, 1H), 3.78 (s, 3H), 2.73 (p, J =7.8 Hz, 1733, C₂₃H₃₃NO₅, 1H), 2.59 (d, J = 12.9 Hz, 1512, 403.2359; 1H),2.49 (s, 1H), 1246, found, 2.28 (t, J = 12.3 Hz, 1H), 1177 403.23471.98-1.70 (m, 10H), 1.65-1.57 (m, 4H), 1.30-1.24 (m, 3H), 1.15 (s, 1H),0.87 (s, 1H) F290 — — ESIMS ¹H NMR (CDCl₃) δ 8.64 (s, ¹⁹F NMR (CDCl₃) δm/z 400 3H), 7.03 (d, J = 8.3 Hz, 2H), −89.67-−89.77 (m) ([M + H]⁺) 6.81(d, J = 8.4 Hz, 2H), 4.89-4.79 (m, 1H), 3.99-3.85 (m, 2H), 3.78 (s, 3H),3.11 (t, J = 9.0 Hz, 1H), 2.96 (d, J = 12.7 Hz, 1H), 2.51-2.36 (m, 1H),2.33-2.09 (m, 3H), 1.75 (s, 1H), 1.73-1.58 (m, 6H), 1.46-1.39 (m, 4H),0.81-0.72 (m, 1H) F291 — — HRMS-ESI ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ(m/z) 8.82-8.25 (br s, 3H), 7.12-6.95 (m, 170.10, 157.88, ([M]⁺) 2H),6.87-6.76 (m, 2H), 132.29, 129.64, calcd for 4.85 (dd, J = 9.1, 6.2 Hz,1H), 113.85, 83.49, 78.87, C₂₁H₃₁NO₄, 3.98-3.89 (m, 1H), 3.78 (s, 3H),76.43, 55.26, 52.16, 361.2253; 3.55 (dd, J = 9.7, 7.0 Hz, 1H), 46.07,35.85, 31.47, found, 3.42 (dd, J = 9.7, 6.8 Hz, 1H), 26.25, 18.13,17.98, 361.2245 3.19-2.97 (m, 2H), 11.15, 3.18, 3.01 2.51-2.37 (m, 1H),2.24 (t, J = 12.5 Hz, 1H), 1.87-1.73 (m, 2H), 1.59-1.38 (m, 3H), 1.42(d, J = 6.4 Hz, 3H), 1.11 (td, J = 7.4, 3.8 Hz, 1H), 0.79-0.68 (m, 1H),0.62-0.43 (m, 2H), 0.24 (dq, J = 7.3, 4.5, 3.1 Hz, 2H) F292 — (ThinHRMS-ESI ¹H NMR (CDCl₃) δ — Film) (m/z) 8.79-8.60 (br s, 3H), 4.96-4.71(m, 3411, ([M]⁺) 1H), 4.10-3.73 (m, 1H), 2943, calcd for 3.48 (dd, J =9.6, 7.0 Hz, 1H), 2869, C₁₉H₃₃NO₃, 3.34 (dd, J = 9.6, 6.9 Hz, 1H), 1746,323.2460; 2.95 (t, J = 8.9 Hz, 1H), 1233, found, 2.68-2.43 (m, 1H),1.87-1.48 (m, 12H), 1070 323.2471 1.49-1.29 (m, 2H), 1.42 (d, J = 6.3Hz, 3H), 1.07 (dt, J = 12.6, 6.8 Hz, 3H), 0.97-0.81 (m, 1H), 0.59-0.48(m, 2H), 0.25-0.16 (m, 2H) F293 — — HRMS-ESI ¹H NMR (CDCl₃) δ 8.61 (brs, ¹³C NMR (CDCl₃) δ (m/z) 3H), 7.03 (d, J = 8.3 Hz, 2H), 170.15,157.86, ([M]⁺) 6.87-6.68 (m, 2H), 4.85 (td, J = 27.2, 132.41, 129.62,calcd for 23.8, 14.0 Hz, 1H), 113.87, 113.84, 83.42, C₂₁H₃₃NO₄, 3.96 (s,1H), 3.78 (s, 3H), 83.33, 80.77, 55.26, 363.2410; 3.56-3.47 (m, 1H),3.31 (t, J = 7.6 Hz, 46.21, 35.67, 29.25, found, 1H), 3.08 (t, J = 9.0Hz, 19.52, 19.47, 18.23, 363.2396 1H), 3.03-2.95 (m, 1H), 18.15, 18.072.76 (br s, 1H), 2.55-2.37 (br s, 1H), 2.23 (t, J = 12.5 Hz, 1H),2.14-1.99 (m, 1H), 1.88 (dt, J = 13.1, 6.6 Hz, 1H), 1.67-1.34 (m, 6H),0.96 (dd, J = 6.7, 5.2 Hz, 6H), 0.76 (s, 1H) F294 — — HRMS-ESI ¹H NMR(CDCl₃) δ 8.61 (s, ¹³C NMR (CDCl₃) δ (m/z) 3H), 7.03 (d, J = 8.5 Hz,2H), 170.13, 157.86, ([M]⁺) 6.88-6.66 (m, 2H), 132.36, 129.63, calcd for4.93-4.75 (m, 1H), 3.96 (d, J = 8.1 Hz, 113.82, 83.68, 75.71, C₂₀H₃₁NO₄,1H), 3.78 (s, 3H), 3.49 (dt, 67.09, 55.25, 52.16, 349.2253; J = 8.7, 6.7Hz, 1H), 3.09 (t, J = 9.1 Hz, 46.08, 35.78, 31.44, found, 1H), 3.00 (d,J = 10.9 Hz, 26.23, 23.57, 18.16, 349.2234 1H), 2.44 (dd, J = 13.3,17.97, 10.73 6.6 Hz, 1H), 2.24 (t, J = 12.5 Hz, 1H), 1.77 (d, J = 23.7Hz, 3H), 1.68-1.51 (m, 3H), 1.43 (t, J = 7.1 Hz, 5H), 0.97 (t, J = 7.4Hz, 3H), 0.74 (d, J = 14.8 Hz, 1H) F295 — (Thin HRMS-ESI ¹H NMR (CDCl₃)δ 8.63 (s, ¹³C NMR (CDCl₃) δ Film) (m/z) 3H), 7.29 (d, J = 1.7 Hz, 1H),170.21, 154.29, 2956, ([M]⁺) 6.26 (dd, J = 3.1, 1.8 Hz, 1H), 141.09,110.13, 2876, calcd for 5.99 (d, J = 3.0 Hz, 1H), 106.15, 83.19, 80.39,1746, C₁₈H₂₉NO₄, 4.89-4.82 (m, 1H), 3.98 (s, 1H), 76.34, 69.65, 52.33,1536, 323.2097; 3.47 (t, J = 7.5 Hz, 1H), 43.11, 31.32, 29.28, 1231,found, 3.28 (t, J = 7.4 Hz, 1H), 3.10 (td, J = 8.9, 29.19, 27.72, 19.47,1207 323.2107 4.7 Hz, 1H), 19.44, 18.08 3.01-2.92 (m, 1H), 2.53-2.37 (m,2H), 2.05 (s, 1H), 1.88 (dp, J = 19.7, 7.9, 6.9 Hz, 2H), 1.60 (d, J =18.9 Hz, 4H), 1.49-1.36 (m, 3H), 0.93 (d, J = 6.6 Hz, 6H) F296 — (ThinHRMS-ESI ¹H NMR (CDCl₃) δ 8.70 (s, — Film) (m/z) 3H), 5.01-4.92 (m, 1H),3392, ([M]⁺) 4.86-4.74 (m, 1H), 4.05 (s, 1H), 2943, calcd for 3.76-3.66(m, 1H), 2871, C₁₉H₃₃NO₄, 2.63-2.49 (m, 1H), 1.81-0.83 (m, 1736,339.2410; 26H) 1455, found, 1187, 339.2409 1153, 1063 F297 — (ThinHRMS-ESI ¹H NMR (CDCl₃) δ 8.71 (s, — Film) (m/z) 1H), 4.92-4.78 (m, 1H),3390, ([M]⁺) 3.69-3.57 (m, 1H), 3.47-3.37 (m, 2942, calcd for 1H), 2.95(t, J = 8.9 Hz, 1H), 2869, C₁₈H₃₃NO₃, 2.86-2.79 (m, 1H), 1744, 311.2460;2.57-2.50 (m, 1H), 1.86-1.31 (m, 1453, found, 19H), 1.15-0.96 (m, 4H),1230, 311.2466 0.93 (t, J = 7.3 Hz, 3H) 1095, 729 F298 — — HRMS-ESI ¹HNMR (CDCl₃) δ 8.68 (s, ¹³C NMR (CDCl₃) δ (m/z) 3H), 4.89-4.75 (m, 1H),170.29, 128.37, 83.94, ([M]⁺) 3.99 (s, 1H), 3.84-3.61 (m, 3H), 80.52,42.30, 37.10, calcd for 3.50-3.41 (m, 1H), 37.06, 36.60, 33.91,C₁₉H₃₅NO₃, 3.27-3.18 (m, 2H), 2.93 (t, J = 8.8 Hz, 31.65, 29.16, 25.09,325.2617; 1H), 2.85-2.79 (m, 1H), 25.05, 19.48, 19.37, found, 2.52 (s,1H), 1.91-1.71 (m, 18.43, 18.28, 18.11, 325.2619 3H), 1.65-1.47 (m, 5H),18.06 1.15-0.85 (m, 14H) F299 — — ESIMS — — m/z 278.2 ([M + H]⁺) F300 —— ESIMS — — m/z 292.2 ([M + H]⁺) F301 — — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR(CD₃OD) δ m/z 334.4 7.31-7.22 (m, 2H), 7.21-7.13 (m, 171.46, 141.99,([M + H]⁺) 3H), 3.98-3.83 (m, 1H), 129.89, 129.46, 3.77-3.70 (m, 1H),3.66 (q, J = 5.5, 127.06, 84.74, 81.69, 5.0 Hz, 1H), 77.66, 53.00,47.35, 3.61-3.53 (m, 1H), 3.41 (dd, J = 8.5, 6.4 Hz, 37.69, 32.11,30.51, 1H), 3.23 (t, J = 8.9 Hz, 28.03, 19.88, 19.83, 1H), 3.10 (dd, J =13.3, 3.4 Hz, 19.45, 18.49 1H), 2.47-2.30 (m, 1H), 2.20 (qd, J = 8.4,7.5, 5.0 Hz, 1H), 1.89 (dt, J = 13.2, 6.6 Hz, 1H), 1.84-1.74 (m, 1H),1.64 (dp, J = 8.5, 3.2, 2.8 Hz, 2H), 1.48 (d, J = 6.4 Hz, 4H), 1.36-1.24(m, 2H), 0.98 (dd, J = 6.7, 3.6 Hz, 6H), 0.95-0.79 (m, 2H) F302 — —ESIMS ¹H NMR (CDCl₃) δ 8.54 (s, ¹³C NMR (CDCl₃) δ m/z 348 3H), 7.18-6.88(m, 4H), 170.32, 137.33, ([M + H]⁺) 4.83 (s, 1H), 4.30-3.82 (m, 1H),135.36, 129.08, 3.62-3.43 (m, 1H), 128.67, 83.50, 80.81, 3.43-3.21 (m,1H), 3.23-2.90 (m, 76.36, 52.63, 46.21, 2H), 2.31 (s, 5H), 1.83 (d, J =41.6 Hz, 36.20, 31.43, 29.28, 2H), 1.68-1.15 (m, 26.16, 21.04, 19.58,7H), 0.96 (t, J = 5.9 Hz, 6H), 19.52, 18.35, 18.22 0.81-0.60 (m, 1H)F303 — — ESIMS ¹H NMR (DMSO-d₆) δ 8.40 (s, ¹³C NMR (DMSO-d₆) m/z 290.23H), 4.91-4.71 (m, 1H), δ 170.43, 83.07, 82.65, ([M + H]⁺) 4.56 (d, J =4.7 Hz, 1H), 4.43 (t, J = 6.0 Hz, 81.46, 78.94, 75.34, 1H), 3.88 (dd, J= 10.4, 51.12, 30.33, 28.51, 6.9 Hz, 1H), 3.42 (dd, J = 8.6, 27.71,19.14, 19.11, 6.6 Hz, 1H), 3.26 (dd, J = 8.6, 17.96, 17.75 6.4 Hz, 1H),3.09 (t, J = 8.6 Hz, 1H), 2.13 (dd, J = 13.2, 6.5 Hz, 1H), 2.05-1.85 (m,1H), 1.86-1.48 (m, 5H), 1.45-1.27 (m, 5H), 0.87 (d, J = 6.7 Hz, 6H) F304210 — ESIMS ¹H NMR (CD₃OD) δ 7.08 (s, ¹³C NMR (CD₃OD) δ (dec) m/z 3464H), 4.87 (s, 1H), 171.19, 138.52, ([M + H]⁺) 4.13-3.42 (m, 3H), 3.30(d, J = 19.1 Hz, 136.24, 129.92, 1H), 3.08 (s, 1H), 2.29 (s, 5H),129.76, 84.73, 79.80, 1.57 (q, J = 58.8, 55.9 Hz, 77.27, 53.39, 47.04,8H), 1.13 (s, 1H), 0.85 (d, J = 11.7 Hz, 37.36, 32.14, 27.85, 1H), 0.56(s, 2H), 21.08, 19.65, 18.63, 0.27 (s, 2H) 11.98, 3.64, 3.63 F305 — —ESIMS — — m/z 384.9 ([M + H]⁺) F306 — — ESIMS — — m/z 321.9 ([M + H]⁺)F307 — — ESIMS — — m/z 318.5 ([M + H]⁺) F308 200-210 ESIMS ¹H NMR(CD₃OD) δ ¹³C NMR (CD₃OD) d (dec) m/z 368 7.44-6.80 (m, 9H), 5.14 (s,1H), 171.05, 160.65, ([M + H]⁺) 4.46 (s, 1H), 3.63 (s, 4H), 137.89,136.19, 2.86 (s, 1H), 2.60-1.14 (m, 12H), 130.75, 129.87, 0.96 (s, 1H)129.75, 122.14, 117.03, 81.89, 76.55, 68.05, 46.67, 37.46, 32.38, 27.71,21.05, 20.12, 18.85 F309 — — ESIMS — — (m/z) 302.3 ([M + H]⁺) F310 — —ESIMS — — (m/z) 272.2 ([M + H]⁺) F311 233-237 — ESIMS 1H NMR (CD₃OD) δ¹³C NMR (101 MHz, m/z 404 7.44-7.25 (m, 5H), 7.24-7.15 (m, CD₃OD) δ171.39, ([M + H]⁺) 1H), 6.92-6.82 (m, 2H), 162.92 (dd, J = 245.6, 4.96(dq, J = 9.4, 6.5 Hz, 1H), 12.2 Hz), 162.52 (dd, J = 246.5, 4.81 (d, J =11.1 Hz, 1H), 4.66 (d, J = 11.2 Hz, 12.1 Hz), 1H), 3.96 (dd, J = 10.9,139.36, 133.26 (dd, J = 9.5, 7.1 Hz, 1H), 3.49 (t, J = 8.9 Hz, 6.7 Hz),129.44, 1H), 3.04 (dd, J = 13.7, 128.93, 128.88, 3.5 Hz, 1H), 2.51 (dd,J = 13.6, 124.57 (dd, J = 15.9, 11.4 Hz, 1H), 3.9 Hz), 112.10 (dd, J =20.9, 2.34-2.20 (m, 1H), 1.88 (ddq, J = 12.1, 3.9 Hz), 8.0, 3.9 Hz, 1H),105.04-103.87 (m), 84.75, 1.74-1.60 (m, 2H), 1.53 (d, J = 6.4 Hz, 77.35,76.41, 52.98, 3H), 1.50-1.40 (m, 1H), 45.56, 32.02, 30.42, 1.35 (dtd, J= 13.3, 10.4, 3.2 Hz, 28.52, 19.46, 18.50 1H), 0.92 (ddt, J = 14.7, ¹⁹FNMR (CD₃OD) δ 6.7, 3.4 Hz, 1H) 61.08 (d, J = 6.4 Hz), 60.97 (d, J = 6.5Hz) F312 — — ESIMS — — (m/z) 370.1 ([M + H]⁺) F313 — — ESIMS — — (m/z)292.2 ([M + H]+) F314 — — ESIMS — — (m/z) 328.5 ([M + H]⁺) F315 — —ESIMS — — (m/z) 340.3 ([M + H]⁺) F316 — — ESIMS ¹H NMR (CDCl₃) δ ¹⁹F NMR(CDCl₃) δ m/z 402 7.31-7.23 (m, 1H), 7.21-7.12 (m, −66.34 (d, J = 3.6Hz) ([M + H]⁺) 2H), 7.08 (d, J = 7.7 Hz, 2H), 6.99 (d, J = 7.8 Hz, 2H),4.98-4.73 (m, 1H), 3.84-3.72 (m, 1H), 3.57 (q, J = 6.9 Hz, 1H), 3.11(dt, J = 8.5, 5.5 Hz, 1H), 2.92 (d, J = 13.4 Hz, 1H), 2.75 (s, 1H),2.58-2.39 (m, 1H), 2.38-2.09 (m, 5H), 1.83 (tt, J = 15.7, 7.5 Hz, 3H),1.72-1.31 (m, 5H), 0.87-0.64 (m, 1H) F317 190-195 — ESIMS ¹H NMR (CDCl₃)δ ¹⁹F NMR (CDCl₃) δ (dec) m/z 432 7.34-7.14 (m, 5H), 7.08 (q, J = 7.9Hz, −113.07 (dd, J = 44.4, ([M + H]⁺) 1H), 6.87-6.71 (m, 2H), 6.6 Hz),−113.76 (dd, J = 21.5, 4.98-4.77 (m, 1H), 6.6 Hz) 3.83-3.71 (m, 1H),3.61-3.48 (m, 1H), 3.21-3.07 (m, 1H), 3.02-2.88 (m, 1H), 2.73 (dp, J =12.2, 3.9 Hz, 3H), 2.57-2.35 (m, 2H), 2.08-1.30 (m, 10H), 0.83 (p, J =11.1, 8.5 Hz, 1H) F318 — — ESIMS — — m/z 362.3 ([M + H]⁺) F319 — — ESIMS— — m/z 214.2 ([M + H]⁺) F320 — — ESIMS — — m/z 290.2 ([M + H]⁺) F32167-73 — ESIMS ¹H NMR (CD₃OD) δ ¹³C NMR (CD₃OD) δ m/z 370 7.19-7.10 (m,1H), 6.98-6.81 (m, 171.35, 162.87 (dd, J = 245.7, ([M + H]⁺) 2H), 3.94(dd, J = 10.8, 7.3 Hz, 12.4 Hz), 1H), 3.65 (s, 3H), 163.88-161.09 (m),3.57 (ddd, J = 8.5, 6.2, 2.6 Hz, 1H), 133.43-133.07 (m), 3.37 (dd, J =8.5, 6.4 Hz, 1H), 124.58 (dd, J = 16.1, 3.24 (td, J = 8.9, 2.7 Hz, 1H),4.1 Hz), 112.10 (dd, J = 20.8, 3.16-2.99 (m, 1H), 3.9 Hz), 2.87-2.68 (m,1H), 2.51 (td, J = 14.2, 104.41 (t, J = 26.1 Hz), 84.49, 13.8, 11.6 Hz,1H), 81.38, 77.43, 52.92, 2.43-2.21 (m, 1H), 1.95-1.25 (m, 47.12, 45.69,32.01, 9H), 1.05 (dd, J = 5.4, 3.3 Hz, 30.33, 19.84, 19.81, 1H), 0.96(d, J = 6.7 Hz, 3H), 19.38, 18.54, 18.42 0.96 (d, J = 6.7 Hz, 3H) ¹⁹FNMR (CD₃OD) δ 61.22 (d, J = 6.5 Hz), 61.11 (d, J = 6.6 Hz) F322 218-222— ESIMS ¹H NMR (CD₃OD) δ 7.79 (dd, ¹³C NMR (CD₃OD) δ dec. m/z 480 J =1.6, 0.6 Hz, 1H), 171.31, 163.00 (dd, J = 245.7, ([M + H]⁺) 7.28-7.22(m, 1H), 7.19 (q, J = 8.3 Hz, 11.9 Hz), 1H), 6.79 (t, J = 8.9 Hz, 162.37(dd, J = 246.5, 2H), 6.66-6.60 (m, 1H), 11.9 Hz), 159.59, 5.22-5.11 (m,2H), 4.04 (dd, J = 10.9, 148.98, 144.99, 7.2 Hz, 1H), 2.72 (dd, J =13.9, 133.20 (dd, J = 9.6, 6.4 Hz), 5.1 Hz, 1H), 2.56 (dd, 123.73 (dd, J= 15.7, J = 13.9, 9.6 Hz, 1H), 2.35 (dt, 3.8 Hz), 120.22, J = 13.3, 6.9Hz, 1H), 113.23, 112.04 (dd, J = 21.2, 2.18 (dq, J = 9.0, 4.5 Hz, 1H),3.7 Hz), 1.90-1.60 (m, 3H), 1.44 (q, J = 12.3, 104.43 (t, J = 26.1 Hz),77.44, 11.8 Hz, 1H), 1.31 (d, J = 5.7 Hz, 75.47, 52.89, 43.74, 3H),1.12-0.99 (m, 31.98, 31.03, 28.52, 1H) 19.19, 17.75 ¹⁹F NMR (CD₃OD) δ61.51 (d, J = 6.8 Hz), 60.95 (d, J = 6.8 Hz) ¹H NMR were run at 400 MHzunless noted otherwise ¹³C NMR were run at 101 MHz unless notedotherwise ¹⁹F NMR were run at 376 MHz unless noted otherwise

TABLE 3 Biological Testing Rating Scale Rating Table for FungalPathogens % Control Rating 80 − 100 A More than 0 − Less than 80 B NotTested C No activity noticed in this bioassay D

TABLE 4 Biological Activity - Disease Control in High and Low VolumeApplications PUCCRT* SEPTTR* 1DP* 3DC* 1DP* 3DC* Rate Rate Cmpd. 121.5100 121.5 100 121.5 100 121.5 100 No. g/H* ppm* g/H* ppm* g/H* ppm* g/H*ppm* F1 C A C B C A C A F2 C A C B C A C A F3 C A C A C A C A F4 C A C AC A C A F5 C A C B C A C A F6 C A C A C A C A F7 C A C B C A C A F8 C AC A C A C A F9 C A C A C A C A F10 A A B A A A A A F11 C A C B C A C AF12 C B C A C A C A F13 C D C B C A C A F14 C A C A C A C A F15 C A C AC A C A F16 C A C B C A C B F17 C A C B C A C A F18 C A C B C A C A F19C A C A C A C A F20 C A C B C A C A F21 C A C A C B C B F22 C A C A C AC A F23 C A C A C A C A F24 C A C A C A C A F25 C A C D C A C B F26 C AC B C A C A F27 C A C A C A C A F28 C A C D C A C B F29 C C C C C C C CF30 C A C A C A C A F31 C A C A C A C A F32 C A C B C A C A F33 C A C AC A C A F34 C A C A C A C A F35 C B C D C A C D F36 C A C D C A C D F37C B C B C A C D F38 C A C A C A C D F39 C A C A C A C B F40 C A C B C BC B F41 C A C B C A C A F42 C A C A C A C A F43 C A C A C A C A F44 C AC A C A C A F45 C A C A C A C A F46 C A C A C B C A F47 C A C A C A C AF48 C A C A C A C A F49 C A C B C A C A F50 C A C A C A C A F51 C A C BC A C B F52 C A C A C A C A F53 C A C A C A C B F54 C A C A C B C A F55C A C D C A C B F56 C A C B C A C B F57 C A C A C A C B F58 C A C A C DC D F59 A A D A A A B A F60 A A D A A A D A F61 C A C B C A C D F62 A AB A A A A A F63 A A A A A A A A F64 A A A A A A A A F65 A A B A A A A AF66 B A B A A A B A F67 A A A A A A A A F68 A A B A A A A A F69 A A A AA A A A F70 A A A A A A A A F71 A A B A A A A A F72 A A B A A A A A F73A A A A A A A A F74 A A B A A A A A F75 A A B A A A A A F76 A C A C A CA C F77 A A A A A A A A F78 A A A A A A A A F79 C A C A C A C A F80 A AA A A A A A F81 A A A A A A A A F82 A A A A A A A A F83 A A A A B A B DF84 A A A A B A D A F85 A C A C B C D C F86 A C A C A C A C F87 A C A CA C A C F88 A C A C A C A C F89 A A B A A A A A F90 A A A A A A A A F91A A A A A A A A F92 A A A A A A A A F93 A A B A A A A A F94 C A C A C AC A F95 A A B A A A B A F96 A A B A A A A A F97 A A A A A A A A F98 A AA A A A A A F99 A A B A A A A A F100 A A B A A A A A F101 A A A A A A AA F102 A A B A A A A A F103 A A A A A A A A F104 A A B A A A A A F105 AD A A A A A A F106 A A A A A A A A F107 A A A A A A A A F108 A A B A A AA A F109 A A A A A A A A F110 A A A A A A A A F111 A C A C A C A C F112A C A C A C A C F113 A A A A A A A A F114 A A B A A A A A F115 A A B A AA A A F116 A A A A A A A A F117 A A A A A A A A F118 A A A A A A A AF119 A A A A A A A A F120 A C D C A C B C F121 A A A A A A A A F122 A AA A A A A A F123 A A B A A A A A F124 A A A A A A A A F125 A A A A A A AA F126 A A B A A A A A F127 C A C A C A C A F128 A A A A A A A A F129 AA B A A A A A F130 A A A A A A A B F131 A A A A B A A A F132 A A A A A AA A F133 A A A A A A A A F134 C A C A C A C A F135 C A C A C A C A F136A A A A A A A A F137 A A B A A A A A F138 A A A A A A A A F139 A A B A AA A A F140 A A A A B A B B F141 A A D B A A B A F142 A A A A A A B AF143 A A A A B B D B F144 A C D C A C B C F145 A C A C A C A C F146 A CA C A C A C F147 A A B A A A A A F148 A A A A A A A A F149 A A A A A A AA F150 A A B A A A A A F151 A A A A A A A A F152 A A A A A A A A F153 AA B A A A A A F154 A A A A A A A A F155 A A A A A A A A F156 A A A A B BB B F157 A C B C A C D C F158 A A B A A A A A F159 A A B A A A A A F160A A A A A A A A F161 A A A A A A A A F162 A A B A A A A A F163 B A B B AA B A F164 A A B A A A A A F165 A A B A A A A A F166 A A A A A A A AF167 A A A A A A A A F168 A A A A A A A A F169 A A A A A A A B F170 A AB A A A A A F171 A A B A A A A A F172 A A A A A A A A F173 A A A A A A AA F174 A A A A A A A A F175 A A B A A A B A F176 A A B A A A A A F177 AA A A A A A A F178 A A B A A A A A F179 A A B A A A A A F180 A A B A A AA A F181 A A A A A A A A F182 A A B A A A A A F183 A A A A A A A A F184C A C A C A C A F185 C A C A C A C A F186 C A C A C A C A F187 A A A A AA A A F188 A A A A A A A A F189 A A A A A A A A F190 A A B D A A A AF191 A A A A B A B D F192 A A A A D D D D F193 A C D C A C B C F194 A AB A A A A A F195 A A B A A A A A F196 A A A A B A B B F197 A C A C A C AC F198 A C A C A C A C *PUCCRT—Wheat Brown Rust (Puccinia triticina)*SEPTTR—Wheat Leaf Blotch (Septoria tritici) *1DP—1 Day Protectant*3DC—3 Day Curative

TABLE 5 Biological Activity—Disease Control at 100 ppm Compound. ALTESO*CERCBE* COLLLA* ERYSCI* ERYSGH* Number 1DP* F64 A A A A A F67 A A A B AF70 B A A A A F78 B A A B B F80 B A A D B F81 B A A B B F82 D A A D BF86 B A A D B F87 A A A B A F88 A A A A A F92 A A A A B F96 A A A A BF98 A A A A A F101 A A A A A F102 C C A C B F106 A A A A A F107 A A A AA F108 D A A D B F109 A A A A A F110 C C C C A F113 A A C A A F114 D A AD C F117 A A A A A F118 B A A B C F119 B A A A C F126 B A A A C F128 A AA B B F130 B B A B B F138 D A A D B F144 A B A B D F145 A A A A A F146 AA A D B F151 A A A A A F152 A A A A A F157 A A A D D F161 A A A A A F164A A A A A F166 D D C D C F167 A A A A A F168 D D A D A F172 A A A A AF173 A A A A A F174 A A A A A F175 A A C B A F181 A B A B B F183 B B A BB F193 A A A D B 198 A A A A A *ALTESO—Tomato Early Blight (Alternariasolani) *CERCBE—Leaf Spot of Sugar Beets (Cercospora beticola)*COLLLA—Cucumber Anthracnose (Glomerella lagenarium; Anamorph:Colletotricum lagenarium) *ERYSCI—Powdery Mildew of Cucumber (Erysiphecichoracearum) *ERYSGH—Barley Powdery Mildew (Blumeria graminis f.sp.hordei; Synonym: Erysiphe graminis f.sp. hordei) 1DP—1 Day Protectant

TABLE 6 Biological Activity - Disease Control at 100 ppm Compound.ERYSGT* LEPTNO* PYRIOR* RHYNSE* UNCINE* VENTIN* Number 1DP* F64 C A A AA B F67 C A A A B B F70 C A A A A B F78 C A A A B B F80 C C A D B B F81C C A A A B F82 C C A B B B F86 C A A A A B F87 C A A A A C F88 C A A AA C F92 C A A A A A F96 C A A A A B F98 C A A A A B F101 C C A A A DF102 C C C C B C F106 A A A A A B F107 C C A A B C F108 C A A A A B F109C A A A A A F110 C A A A A B F113 C C A A B C F114 C C A A C C F117 C AA A A A F118 C C A A C C F119 C C A A C C F126 C C A A C C F128 C A A BA B F130 C A A A B B F138 C C A B B B F144 C A C A B A F145 C A C A A AF146 C A A A A A F151 A A A C C B F152 C C A A B C F157 C A C A A B F161C A A A A A F164 C A A A A A F166 C C D D C D F167 C C A A A A F168 C CD D A D F172 C A A A B B F173 C C A A B C F174 C A A A A A F175 C C A AB C F181 C A A B B D F183 C A A A A B F193 C A A A B A F198 C A A A A C*ERYSGT—Wheat Powdery Mildew (Blumeria graminis f.sp. tritici; Synonym:Erysiphe graminis f.sp. tritici) *LEPTNO—Wheat Glume Blotch(Leptosphaeria nodorum) *PYRIOR—Rice Blast (Magnaporthe grisea;Anamorph: Pyricularia oryzae) *RHYNSE—Barley Scald (Rhyncosporiumsecalis) *UNCINE—Grape Powdery Mildew (Uncinula necator) *VENTIN—AppleScab (Venturia inaequalis) *1DP—1 Day Protectant

TABLE 7 Biological Activity—Disease Control at 25 ppm Compound PHAKPA*Number 1DP* 3DC* F63 A A F64 A A F67 A B F70 A B F76 A A F78 A A F80 A BF81 A A F82 A A F86 A B F91 A A F92 A A F93 A B F96 A B F98 A A F101 A BF106 A B F107 A A F109 A B F113 A B F117 A A F118 A B F119 A B F121 A BF124 A A F128 A A F130 A A F132 A A F138 A A F144 B D F145 A B F146 A AF149 A B F151 A A F152 A A F155 A A F157 B D F160 A A F161 A A F164 A BF166 A B F167 A B F168 A B F172 A B F173 A A F174 A B F181 A A F183 A AF187 A A F189 A A 193 B B *PHAKPA—Asian Soybean Rust (Phakopsorapachyrhizi) *1DP—1 Day Protectant *3DC—3 Day Curative

What is claimed is:
 1. A compound of Formula I

wherein: X is H, C(O)R₃, or CH₂OR₃; Y is H, C(O)R₃, or Q; Q is

R₁ is chosen from H, alkyl, alkenyl, aryl, —Si(R₅)₃, or —C(O)R₆, each optionally substituted with 0, 1 or multiple R₆; R₂ is chosen from CH₂R₈, aryl, alkyl, or alkenyl, each optionally substituted with 0, 1, or multiple R₆; R₃ is chosen from alkyl, alkoxy, benzyl, or benzyloxy, each optionally substituted with 0, 1, or multiple R₅; R₄ is chosen from H, —C(O)R₇ or —CH₂OC(O)R₇; R₅ is chosen from alkyl, halo, or alkoxy; R₆ is chosen from alkyl, alkenyl, halo, haloalkyl, alkoxy, aryl, heteroaryl, heterocyclyl, thioalkyl, or —C(O)R₅; R₇ is chosen from alkyl or alkoxy, each optionally substituted with 0, 1, or multiple R₆; R₈ is chosen from H, alkyl, alkenyl, aryl, thioalkyl, or heteroaryl, each optionally substituted with 0, 1, or multiple R₆.
 2. The compound according to claim 1, wherein X and Y are independently chosen from H, C(O)R₃, or CH₂OR₃.
 3. The compound according to claim 2, wherein R₁ is chosen from H, alkyl, alkenyl, aryl, —Si(R₅)₃, or —C(O)R₆, each optionally substituted with 0, 1 or multiple R₆.
 4. The compound according to claim 3, wherein R₂ is chosen from CH₂R₈, aryl, alkyl, or alkenyl, each optionally substituted with 0, 1, or multiple R₆.
 5. The compound according to claim 4, wherein R₈ is chosen from H, alkyl, alkenyl, aryl, or heteroaryl, each optionally substituted with 0, 1, or multiple R₆.
 6. The compound according to claim 1, wherein X is H and Y is Q.
 7. The compound according to claim 6, wherein R₁ is chosen from H, alkyl, alkenyl, aryl, —Si(R₅)₃, or —C(O)R₆, each optionally substituted with 0, 1 or multiple R₆.
 8. The compound according to claim 7, wherein R₂ is chosen from CH₂R₈, aryl, alkyl, or alkenyl, each optionally substituted with 0, 1, or multiple R₆.
 9. The compound according to claim 8, wherein R₈ is chosen from H, alkyl, alkenyl, aryl, or heteroaryl, each optionally substituted with 0, 1, or multiple R₆.
 10. The compound according to claim 9, wherein R₄ is H, —C(O)R_(D) or —CH₂OC(O)R₇.
 11. The compound according to claim 10, wherein R₄ is chosen from —C(O)R₇ or —CH₂OC(O)R₇.
 12. The compound according to claim 11, wherein R₇ is chosen from alkyl or alkoxy, each optionally substituted with 0, 1, or multiple R₆.
 13. A formulation for the control of a fungal pathogen, comprising: at least one of the compounds of claim 1; and a phytologically acceptable carrier material.
 14. The formulation according to claim 13, wherein the formulation is suitable for treating plants.
 15. A formulation for the control of a fungal pathogen, comprising: at least one of the compounds of claim 1; and at least one agriculturally active ingredient selected from the group consisting of: fungicides, insecticides, nematocides, miticides, arthropodicides, bactericides and combinations thereof.
 16. The formulation according to claim 15, wherein the formulation is suitable for treating plants.
 17. A formulation for the control of a fungal pathogen, comprising: the formulation of claim 13; and at least one agriculturally active ingredient selected from the group consisting of: fungicides, insecticides, nematocides, miticides, arthropodicides, bactericides and combinations thereof.
 18. The formulation according to claim 14, wherein the formulation is suitable for treating plants. 